CN108140586A - The forming method of thermosetting resin film, the 1st protective film formation piece and the 1st protective film - Google Patents

The forming method of thermosetting resin film, the 1st protective film formation piece and the 1st protective film Download PDF

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Publication number
CN108140586A
CN108140586A CN201680061246.7A CN201680061246A CN108140586A CN 108140586 A CN108140586 A CN 108140586A CN 201680061246 A CN201680061246 A CN 201680061246A CN 108140586 A CN108140586 A CN 108140586A
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China
Prior art keywords
mentioned
methyl
resin
protective film
acrylate
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山岸正宪
佐藤明德
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Lintec Corp
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Lintec Corp
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Publication of CN108140586A publication Critical patent/CN108140586A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/11—Manufacturing methods

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  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Adhesive Tapes (AREA)
  • Encapsulation Of And Coatings For Semiconductor Or Solid State Devices (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

Abstract

The present invention relates to a kind of thermosetting resin films; its surface with convex block for being used to be pasted onto semiconductor wafer simultaneously forms the 1st protective film by carrying out heat cure on above-mentioned surface; when the thermosetting resin film before curing is made to heat up with 10 DEG C/minute of heating rate, the film is in shear velocity 1s‑1Under viscosity reach below 100000Pas time be 500 seconds or more.1st protective film formation piece of the present invention has the 1st support chip, and has the thermosetting resin film on a side surface of the 1st support chip.By bringing it about heat cure while pressurizeing to the thermosetting resin film with the pressure of more than 0.1Pa, so as to form the 1st protective film.

Description

The forming method of thermosetting resin film, the 1st protective film formation piece and the 1st protective film
Technical field
The present invention relates to thermosetting resin film and the 1st protective film formation piece of above-mentioned thermosetting resin film is used And the 1st protective film forming method.
The application is preferential in No. 2015-217117 requirement of Japanese Patent Application that Japan files an application based on November 4th, 2015 Power, and its content is incorporated herein.
Background technology
In the past, it in the case where the more pin LSI packaging bodies for being used for MPU, gate array etc. are installed on printed circuit board, adopts The flip-chip installation method being discussed further below：As semiconductor chip, it is formed with using welding disk is connected at it by altogether The semiconductor chip of convex electrode (convex block) made of brilliant solder, high-temperature solder, gold etc., by so-called upside-down mounting mode, makes these convex Block is opposed with the corresponding portion of terminal on chip carrying substrate, contacts, and carries out melting/spreading engagement.
The semiconductor chip used in the installation method can for example pass through the semiconductor to being formed with convex block in circuit face Chip is ground with the face of circuit face opposite side or is cut so that monolithic is made and obtained.Half is obtained such During conductor chip, in general, in order to achieve the purpose that the circuit face and convex block of protection semiconductor wafer, in convex block forming face It pastes curable resin film and the film is made to cure and form protective film in convex block forming face.As such curable resin Film, what is be widely used is containing by heating and the resin film of cured thermosetting component, as having such thermosetting Property resin film protective film formation piece, it has been disclosed that on above-mentioned film be laminated with specific high-temperature elastic modulus thermoplasticity It is aplastic thermoplastic resin layer that resin layer and the further top layer in above-mentioned thermoplastic resin layer, which are layered at 25 DEG C, The sheet material formed (referring to patent document 1).According to patent document 1, the convex block fillibility of the protective film of the protective film formation piece, Reliability of electrical connection after chip processability, resin seal etc. is excellent.
However, there are following problems in some cases for the protective film formed by thermosetting resin film：Sometimes wherein Contain bubble.If there are bubble in protective film, can thus lead to convex block forming face and the adaptation of protective film reduce or Relative to protective film circuit face and convex block protective capability decline etc. cause protective film that can not fully give play to its function Possibility.If in addition, there are bubbles in protective film, in the protective film because Reflow Soldering is when being heated, meeting is swollen because of bubble It is swollen and convex block forming face and the adaptation of protective film is caused to reduce, in the case where bubble drastically expands, can be ruptured because of protective film And cause protective film that the broken of semiconductor chip is detached or for representative occurred with circuit face, convex block etc. with semiconductor chip Damage.Also, for the protective film disclosed in patent document 1, it is also uncertain that whether can inhibit containing for bubble.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2005-028734 bulletins
Invention content
Problems to be solved by the invention
The purpose of the present invention is to provide can contain the protective film inhibited in convex block forming face formation bubble Thermosetting resin film and used the protective film formation piece of above-mentioned thermosetting resin film and the forming method of protective film.
Solution to the problem
The present invention provides a kind of thermosetting resin film, is used to be pasted onto the surface with convex block of semiconductor wafer and leads to Cross carry out heat cure and form the 1st protective film on above-mentioned surface, wherein, make above-mentioned thermosetting resin film before curing with 10 DEG C/ During the heating rate heating divided, in shear velocity 1s-1Under viscosity reach time of below 100000Pas for 500 seconds with On.
In addition, the present invention provides the 1st protective film for having above-mentioned thermosetting resin film on a side surface of the 1st support chip Formation piece.
In addition, the present invention provides the forming method of the 1st protective film, this method includes：By to above-mentioned thermosetting resin Film is brought it about heat cure while pressurization with the pressure of more than 0.1Pa and forms the 1st protective film.
The effect of invention
By using the thermosetting resin film and the 1st protective film formation piece of the present invention, in addition, by using the present invention's The forming method of protective film can contain the protective film inhibited in convex block forming face formation bubble.
Description of the drawings
[Fig. 1] is to schematically show to form the 1st guarantor in convex block forming face using the thermosetting resin film of the present invention The sectional view of an example of the state of cuticula.
[Fig. 2] is to schematically show to form protective film in convex block forming face using traditional thermosetting resin film The sectional view of an example of state.
[Fig. 3] is the sectional view for an embodiment for schematically showing the 1st protective film formation piece of the present invention.
[Fig. 4] is the sectional view for the other embodiment for schematically showing the 1st protective film formation piece of the present invention.
[Fig. 5] is the sectional view for another embodiment for schematically showing the 1st protective film formation piece of the present invention.
[Fig. 6] is the heating time for showing Examples 1 to 2 and the sample in comparative example 1, temperature and shear viscosity (V1) Relationship coordinate diagram.
Symbol description
1st, 2,3 ... the 1st protective film formation piece
11 ... the 1st base materials
The surface of the 1st base materials of 11a ...
12 ... thermoset resin layers (thermosetting resin film)
12 ' ... the 1st protective films
13 ... the 1st adhesive phases
The surface of the 1st adhesive phases of 13a ...
14 ... the 1st middle layers
101st, 102,103 ... the 1st support chip
The surface of the 1st support chip of 101a, 102a, 103a ...
90 ... semiconductor wafers
The circuit face of 90a ... semiconductor wafers
91 ... convex blocks
The surface of 91a ... convex blocks
Specific embodiment
The thermosetting resin film of the present invention is for being pasted onto the surface with convex block of semiconductor wafer and passing through progress Heat cure and above-mentioned surface formed the 1st protective film thermosetting resin film, wherein, make above-mentioned thermosetting resin film before curing When being heated up with 10 DEG C/minute of heating rate, in shear velocity 1s-1Under viscosity reach below 100000Pas time be 500 Second or more.
In addition, the 1st protective film formation of the present invention is to have this above-mentioned hair on a side surface of the 1st support chip with piece The sheet material of bright thermosetting resin film.In above-mentioned 1st protective film formation piece, above-mentioned " thermosetting resin film " is also referred to as " heat Thermosetting resin layer ".
The 1st protective film formation piece of the present invention can be pasted onto half via its thermoset resin layer (thermosetting resin film) The surface (i.e. circuit face) with convex block of conductor chip uses.Wherein, the thermoset resin layer after stickup is heated and flows Dynamic property increase, is extended in a manner of covering convex block between convex block, closely sealed with foregoing circuit face while the surface of covering convex block, The surface at position, convex block is embedded to particularly near foregoing circuit face.The thermoset resin layer of the state is through further heating Heat cure can occur and ultimately form the 1st protective film, convex block is protected to be sealed at the state on its surface in foregoing circuit face.It is just viscous For having pasted the semiconductor wafer after the 1st protective film formation piece, for example, with the face of foregoing circuit face opposite side through overground After cutting, the 1st support chip is removed, and then, the embedment of convex block and the 1st protective film is carried out by heating thermoset resin layer It is formed, is finally assembled in semiconductor device to have the state of the 1st protective film.
It should be noted that in the present specification, the circuit face of lug surface and semiconductor wafer is also referred to as " convex block Forming face ".
As described above, the present invention thermosetting resin film (thermoset resin layer) be since state before curing with 10 DEG C/minute heating rate heating when, shear velocity 1s-1Under viscosity (hereinafter also referred to as " shear viscosity (V1) ") reach The time (hereinafter also referred to as " Δ t1 ") of below 100000Pas is the resin film of 500 seconds or more.That is, the thermosetting of the present invention Property resin film before curing in the state of, when being heated in a manner of meeting above-mentioned heating rate, temporarily first soften and shear viscosity (V1) it reduces, then, shear viscosity (V1) switchs to increase, and ultimately forms the 1st protective film as solidfied material.Wherein, in this way Shear viscosity (V1) reduce after switch to increased time-bands, show the such low-shear viscosities of below 100000Pas (V1), also, the low-shear viscosity (V1) can keep 500 seconds or more such long periods.The thermosetting resin of the present invention Film during low-shear viscosity (V1) is kept for a long time in this wise, the bubble that contain fully the stage before curing (gap) penetrates in the inside of thermosetting resin film itself and is discharged into outside, so as at the time of end is cured, reach basic Go up or be entirely free of bladdery state.It should be noted that in the present specification, contain in thermosetting resin film before curing Bubble also include being present in bubble between thermosetting resin film and convex block forming face.
Therefore, in the case of the thermosetting resin film for using the present invention, the 1st protective film is also finally substantially or entirely Without bladdery, therefore, the 1st protective film, which is based only on this, can give full play of its function, including：Convex block forming face and the Adaptation height, the 1st protective film between 1 protective film is to protective capability height of circuit face and convex block etc..In addition, even if the 1st protects Because Reflow Soldering etc. is heated, the expansion of bubble also will not occur or be inhibited completely, therefore can inhibit convex block forming face cuticula The reduction of adaptation between the 1st protective film, the rupture of the 1st protective film can keep the protective capability of the 1st protective film, can press down The breakage of semiconductor chip processed.In this way, by using the thermosetting resin film of the present invention, using the 1st protective film fully Position, i.e. base portion near the circuit face of circuit face and convex block is protected.
Fig. 1 is to schematically show to form the 1st protection in convex block forming face using the thermosetting resin film of the present invention The sectional view of an example of the state of film.It should be noted that in the following description in used figure, in order to make the present invention's Feature is readily appreciated that, sometimes to ask the convenient part enlargedly shown as major part, the dimensional ratios of each integral part Deng not necessarily identical with actual conditions.
On the circuit face 90a of semiconductor wafer 90 shown here, it is provided with multiple convex blocks 91.Convex block 91 has ball The shape that is cut by plane of a part, be equivalent to the plane at the position for being cut and exposing and semiconductor wafer 90 Circuit face 90a is contacted.
1st protective film 12 ' is formed using the thermosetting resin film of the present invention, coats the electricity of semiconductor wafer 90 Road surface 90a, and be coated in the surface 91a of convex block 91 except the vertex and its region other than around of convex block 91.Like this Ground, the 1st protective film 12 ' be sealed at convex block 91 except vertex and its surface 91a other than around, while also with semiconductor wafer 90 Circuit face 90a it is closely sealed, so that convex block 91 be embedded to.
In the above-mentioned surface 91a of the convex block 91 and circuit face 90a of semiconductor wafer 90, i.e. convex block forming face and the 1st protection Between film 12 ', there is no bubbles, and bubble is also not present in the inside of the 1st protective film 12 '.Convex block 91 it is such substantially spherical Shape be particularly advantageous for bubble is containing the formation of the 1st protective film being inhibited.
In addition, convex block 91 relative to the diameter on direction parallel foregoing circuit face 90a with the distance of convex block 91 The height of lowest part (in other words, with the contact site of foregoing circuit face 90a) is increased and is increased, and after maximum is reached, switchs to subtract It is few.That is, in space in convex block forming face, by the surface of the base portion (position near the 90a of foregoing circuit face) of convex block 91 The space that 91a and foregoing circuit face 90a are clipped becomes especially narrow, and with the lowest part of convex block 91 close to then becoming to get over It is narrow.In such space, it is difficult to fill the bubble in protective film or protective film and be difficult to escape, thus be particularly easy to remaining gas Bubble.
But by using the thermosetting resin film of the present invention, even if in space narrow in this way can realize gas Containing for bubble has obtained the 1st protective film 12 ' of abundant inhibition.Therefore, the 1st protection can fully be obtained from the base portion in convex block 91 It sets out in terms of the protective effect of film 12 ', the substantially spherical shape as described above of convex block 91 is particularly advantageous.
It should be noted that it is not limited to as thermosetting resin film of the invention using the semiconductor wafer of object Structure shown in FIG. 1, in the range of effect of the present invention is not destroyed or its part composition is altered, eliminates or adds The semiconductor wafer formed.For example, in Fig. 1, shown as convex block be essentially as described above spherical shape (ball The shape that a part is cut by plane) convex block, but as the convex block of preferable shape, can also enumerate：It will be such basic It is elongated for spherical shape along short transverse (direction orthogonal for the circuit face 90a relative to semiconductor wafer 90 in Fig. 1) The shape formed, that is, (rotational ellipsoid as long ball includes long axis side to the shape of the rotational ellipsoid as substantially long ball To one end the shape that is cut by plane of position) convex block；It will be essentially spherical shape as described above along height Flatten the shape formed in direction, that is, the shape (packet of the rotational ellipsoid as oblate spheroid of the rotational ellipsoid as substantially oblate spheroid The shape that the position of one end containing short-axis direction is cut by plane) convex block.The shape of such substantially rotational ellipsoid Convex block also contain the formation of the 1st protective film being inhibited similarly, for bubble with above-mentioned substantially spherical convex block It is particularly advantageous.
It should be noted that the shape of illustrated convex block is only to be applicable in the thermosetting resin film of the present invention so far When preferred an example, in the present invention, the shape of convex block is not limited to these shapes.
On the other hand, Fig. 2 is to schematically show to form in convex block forming face using traditional thermosetting resin film The sectional view of an example of the state of protective film.It should be noted that in fig. 2, it will for composition same as shown in Figure 1 Element imparts the symbol being identical with the situation of fig. 1, and its detailed description is omitted.
Protective film 92 ' depicted herein is formed using traditional thermosetting resin film.In the interior of protective film 92 ' Portion, there are bubble 8, also, in the above-mentioned surface 91a of the convex block 91 or circuit face 90a of semiconductor wafer 90, i.e. convex block forming face Between protective film 92 ', there is also bubbles 8.Particularly, between the surface 91a of the base portion of convex block 91 and protective film 92 ', hold Easily there are bubbles 8.In addition, in the protective film at position clipped by the surface 91a of the base portion of convex block 91 and foregoing circuit face 90a In 92 ', easy entrapped air pockets 8.
As described above, the thermosetting resin film of the present invention is with 10 DEG C/minute of heating rate liter before its curing The resin film of Wen Shi, Δ t1 at 500 seconds or more for Δ t1, such as can contain ingredient according to the aftermentioned of thermosetting resin film Type and amount and be adjusted.
The Δ t1 of the thermosetting resin film of the present invention is preferably 520 seconds or more, for example, can be 540 seconds or more, 560 seconds Above, 580 seconds or more, 600 seconds or more, 620 seconds or more and 640 seconds are with the random time in first-class.
On the other hand, the upper limit value of the Δ t1 of thermosetting resin film of the invention is not particularly limited.From thermosetting resin Film have it is good it is heat cured from the aspect of, Δ t1 is preferably less than 10000 seconds, more preferably less than 5000 seconds, it is further Preferably less than 3000 seconds, particularly preferably less than 2000 seconds or such as less than 1000 seconds.
As described above, the thermosetting resin film of the present invention is heated up before its curing with 10 DEG C/minute of heating rate When, temporarily first soften and shear viscosity (V1) reduction, in a period of 500 seconds or more, shear viscosity (V1) is in 100000Pas Below.The lower limiting value of shear viscosity (V1) that the thermosetting resin film of the present invention is shown in such temperature-rise period is not special It limits, but preferably 3000Pas, more preferably 6000Pas, particularly preferably 9000Pas.
For when the thermosetting resin film before curing of the present invention is made to heat up with 10 DEG C/minute of heating rate, shearing is viscous The lower limiting value of temperature that degree reaches the thermosetting resin film of below 100000Pas is not particularly limited, but preferably 60 DEG C, more Preferably 65 DEG C, particularly preferably 70 DEG C.
For when the thermosetting resin film of the present invention is made to heat up with 10 DEG C/minute of heating rate, shear viscosity reaches The upper limit value of the temperature of the thermosetting resin film of below 100000Pas is not particularly limited, but preferably 160 DEG C, more preferably It is 150 DEG C, particularly preferably 140 DEG C.
By making the above-mentioned temperature of thermosetting resin film, in such range, the 1st protective film of inhibition contains bladdery effect It further improves.
It should be noted that in the present invention, the heating rate for determining thermosetting resin film during Δ t1 is 10 DEG C/minute, but Even if 100000Pa is reached with the determination of heating rate shear viscosity other than 10 DEG C/minute of such as 9.8~10.2 DEG C/minute or so The time of below s, time generally also will not there are significant differences with Δ t1.
It is preferred that after the thermosetting resin film before curing of the present invention is pasted on the convex block forming face of semiconductor wafer, Heat cure is brought it about in pressurization, its mobility increase (that is, bringing it about softening) is more preferably made by convex block by heating Embedment further brings it about heat cure and when forming 1 protective film, is carried out at the same time pressurization by heating.In this way, by Make to pressurize during its curing based on heating, the 1st protective film is inhibited to be further improved containing bladdery effect.
Pressure applied is suitably adjusted when carrying out the softening and curing based on heating to the thermosetting resin film of the present invention , but preferably more than 0.1Pa, more preferably 0.1MPa~1MPa, further preferably 0.2MPa~0.8MPa, especially excellent It is selected as 0.4MPa~0.6MPa.By making above-mentioned pressure more than above-mentioned lower limiting value, the 1st protective film is inhibited to contain bladdery effect It further improves, by making above-mentioned pressure in above-mentioned upper limit value hereinafter, inhibiting the breakage in the foregoing circuit face of semiconductor wafer Effect further improves.
To the present invention thermosetting resin film before curing carry out the softening and curing based on heating when, preferably by by its It is placed in gas-pressurized atmosphere and pressurizes.So, it can easily pressurize to thermosetting resin film.
By heating temperature when heating the thermosetting resin film generation softening and curing to make the present invention according to thermosetting property Type of resin film etc. is suitably adjusted, but preferably 60~200 DEG C.
Hereinafter, it is described in detail for the composition of the present invention.
The 1st support chips of ◎
Above-mentioned 1st support chip can be made of 1 layer (individual layer), can also be made of 2 layers or more of multilayer.Support chip is by more In the case that layer is formed, the constituent material and thickness of the multilayer mutually can be the same or different, the combination for the multilayer, It is not particularly limited in the range of effect of the present invention is not destroyed.
It should be noted that in the present specification, being not limited only to the situation of the 1st support chip, " multilayer mutually can be identical Can be different " refer to " both can whole layer all sames, can also all layer it is different, can also only part layer it is identical ", into one Step, " multilayer is mutually different " refers to " at least one of constituent material and thickness of each layer are mutually different ".
As preferred 1st support chip, it can be mentioned, for example：The sheet material that the 1st adhesive phase forms is laminated on the 1st base material； The 1st middle layer is laminated on the 1st base material and the sheet material that the 1st adhesive phase forms is laminated in above-mentioned 1st middle layer；Only by the 1st Sheet material that base material is formed etc..
For the various species of such 1st support chip, with reference to attached drawing to the example of the 1st protective film formation piece of the present invention Son illustrates.
Fig. 3 is the sectional view for an embodiment for schematically showing the 1st protective film formation piece of the present invention.This In shown in the 1st protective film formed in piece 1, as the 1st support chip, use the 1st adhesive phase of stacking on the 1st base material The sheet material formed.That is, the 1st protective film formation piece 1 has the 1st adhesive phase 13 and in the 1st adhesive on the 1st base material 11 Have thermoset resin layer (thermosetting resin film) 12 on layer 13 and form.1st support chip 101 is the bonding of the 1st base material the 11 and the 1st The laminated body of oxidant layer 13, on a side surface 101a of the 1st support chip 101, i.e. in a side surface 13a of the 1st adhesive phase 13 On, it is provided with thermoset resin layer 12.
In the 1st protective film formation in piece 1, thermoset resin layer 12 as described above, with 10 before its curing DEG C/minute heating rate heating when, Δ t1 be 500 seconds or more.
Fig. 4 is the sectional view for the other embodiment for schematically showing the 1st protective film formation piece of the present invention.It needs It is noted that in Fig. 4, for inscape same as shown in Figure 3, the symbol identical with the situation of Fig. 3 is imparted, And description is omitted.This is also same in the figure after Fig. 5.
1st protective film depicted herein is formed in piece 2, as the 1st support chip, is used and is laminated on the 1st base material Simultaneously the sheet material that the 1st adhesive phase forms is laminated in 1st middle layer in above-mentioned 1st middle layer.That is, the 1st protective film is formed with piece 2 Have the 1st middle layer 14 on the 1st base material 11, have the 1st adhesive phase 13 and in the 1st adhesive phase in the 1st middle layer 14 Have thermoset resin layer (thermosetting resin film) 12 on 13 and form.1st support chip 102 is the 1st base material 11, the 1st middle layer The laminated body that 14 and the 1st adhesive phase 13 stacks gradually, on a side surface 102a of the 1st support chip 102, i.e. the 1st On one side surface 13a of adhesive phase 13, it is provided with thermoset resin layer 12.
In other words, the 1st protective film formation piece 2 is in the 1st base material 11 in the 1st protective film formation piece 1 shown in Fig. 3 It is further equipped with obtained from the 1st middle layer 14 between the 1st adhesive phase 13.
In the 1st protective film formation in piece 2, thermoset resin layer 12 as described above, with 10 before its curing DEG C/minute heating rate heating when, Δ t1 be 500 seconds or more.
Fig. 5 is the sectional view for another embodiment for schematically showing the 1st protective film formation piece of the present invention.
1st protective film depicted herein is formed in piece 3, as the 1st support chip, is used and is only made of the 1st base material Sheet material.That is, the 1st protective film formation piece 3 has thermoset resin layer (thermosetting resin film) 12 on the 1st base material 11 and structure Into.1st support chip 103 is only made of the 1st base material 11, on a side surface 103a of the 1st support chip 103, i.e. in the 1st base material 11 A side surface 11a on, be directly contact provided with thermoset resin layer 12.
In other words, the 1st protective film formation is that the 1st protective film formation shown in Fig. 3 is viscous with eliminating the 1st in piece 1 with piece 3 What mixture layer 13 formed.
In the 1st protective film formation in piece 3, thermoset resin layer 12 as described above, with 10 before its curing DEG C/minute heating rate heating when, Δ t1 be 500 seconds or more.
Hereinafter, it is described in detail for the composition of the 1st support chip.
0 the 1st base material
Above-mentioned 1st base material is sheet or membranaceous, and as its constituent material, it can be mentioned, for example various resins.
As above-mentioned resin, it can be mentioned, for example：Low density polyethylene (LDPE) (LDPE), straight-chain low density polyethylene (LLDPE), height The polyethylene such as density polyethylene (HDPE)；The poly- second such as polypropylene, polybutene, polybutadiene, polymethylpentene, norbornene resin Polyolefin other than alkene；Vinyl-vinyl acetate copolymer, ethylene-(methyl) acrylic copolymer, ethylene-(methyl) propylene The ethene copolymers such as acid ester copolymer, ethylene-norbornene copolymer (use ethylene as copolymer obtained from monomer)； The vinyl chloride resins such as polyvinyl chloride, vinyl chloride copolymer (use vinyl chloride as resin obtained from monomer)；Polystyrene； Polycyclic alkene；Polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate (PBT), poly- isophthalic Naphthalate, poly- 2,6- (ethylene naphthalate)s, whole Component units have the full fragrance of aromatic series ring type group The polyester such as adoption ester；The copolymer of two or more above-mentioned polyester；Poly- (methyl) acrylate；Polyurethane；Urethane acrylate； Polyimides；Polyamide；Makrolon；Fluororesin；Polyacetals；Noryl；Polyphenylene sulfide；Polysulfones；Polyether-ketone etc..
In addition, as above-mentioned resin, also it can be mentioned, for example：The polymerizations such as the mixture of above-mentioned polyester and the resin in addition to it Object alloy.For the polymer alloy of above-mentioned polyester and the resin in addition to it, the amount of the resin preferably other than polyester be compared with On a small quantity.
In addition, as above-mentioned resin, also it can be mentioned, for example：One or more of above-mentioned resin that example goes out before this It is crosslinked the crosslinked resin formed；Use ionomer of one or more of the above-mentioned resin that example goes out before this etc. modified Resin.
It should be noted that in the present specification, " (methyl) acrylic acid " is to include " acrylic acid " and " methacrylic acid " The concept of the two.About also the same with term as (methyl) acrylic compounds, for example, " (methyl) acrylate " is to include The concept of both " acrylate " and " methacrylate ", " (methyl) acryloyl group " is to include " acryloyl group " and " first The concept of both base acryloyl groups ".
It can be only a kind of or two or more to form the resin of the 1st base material, in the case of being two or more, it Combination and ratio can arbitrarily select.
1st base material can be only one layer (individual layer) or more than two layers of multilayer, and in the case of being multilayer, this is more Layer mutually can be the same or different, and the combination of the multilayer is not particularly limited.
The thickness of 1st base material is preferably 5~1000 μm, more preferably 10~500 μm, further preferably 15~300 μm, Particularly preferably 20~150 μm.
Here, " thickness of the 1st base material " represents the thickness of the 1st base material entirety, for example, the 1st base material being made up of multiple layers Thickness refers to form the aggregate thickness of whole layers of the 1st base material.
1st base material is preferably the high material of thickness and precision, can inhibit the uneven material of thickness independent of position. The material that can be used in form 1st base material high as such thickness and precision in above-mentioned constituent material, it can be mentioned, for example：It is poly- Ethylene, the polyolefin in addition to polyethylene, polyethylene terephthalate, vinyl-vinyl acetate copolymer etc..
In 1st base material other than the main constituent material such as above-mentioned resin, can also contain packing material, colorant, Various additives well known to antistatic agent, antioxidant, organic lubricant, catalyst, softening agent (plasticizer) etc..
1st base material can be it is transparent can also be it is opaque, according to purpose, can be by coloring, can also Vapor deposition has other layers.
In the case that the 1st adhesive phase or curable resin layer being described below have energy ray-curable, the 1st base material The material for preferably penetrating energy line.
1st base material can utilize well known method to manufacture.For example, the 1st base material containing resin can be by that will contain above-mentioned tree The resin combination of fat is molded and is manufactured.
0 the 1st adhesive phase
Above-mentioned 1st adhesive phase is sheet or membranaceous, contains adhesive.
As above-mentioned adhesive, it can be mentioned, for example：Acrylic resin (is made of the resin with (methyl) acryloyl group Adhesive), urethane based resin (adhesive made of the resin with amino-formate bond), rubber resin (adhesive made of the resin with rubber structure), organic silicon resin (glue made of the resin with siloxanes key Mixture), epoxylite (adhesive made of the resin with epoxy group), polyvingl ether, the adhesiveness such as makrolon Resin, preferably acrylic resin.
It should be noted that in the present invention, " resin of binding property " is to include resin with adhesiveness and with bonding Property both resins concept, not only including such as resin itself has a case that adhesiveness, further include by with additive It is applied in combination etc. other ingredients and shows the resin of adhesiveness, shown due to the presence of the triggering factor such as heat or water (trigger) Show resin of cementability etc..
1st adhesive phase can be only one layer (individual layer) or more than two layers of multilayer, in the case of being multilayer, The multilayer mutually can be the same or different, and the combination of the multilayer is not particularly limited.
The thickness of 1st adhesive phase is preferably 1~1000 μm, more preferably 5~500 μm, particularly preferably 10~100 μ m。
Here, " thickness of the 1st adhesive phase " represents the thickness of the 1st adhesive phase entirety, for example, be made up of multiple layers the The thickness of 1 adhesive phase refers to form the aggregate thickness of whole layers of the 1st adhesive phase.
1st adhesive phase can be the layer formed using energy ray-curable adhesive or use non-energy line The layer that curing adhesive is formed.The 1st adhesive phase formed for using the adhesive of energy ray-curable, can be easy Ground adjusts the physical property after curing preceding and curing.
In the present invention, " energy line " refers to the electromagnetic wave or charged particle beam with the quantum of energy, as its example, can arrange Lift ultraviolet light, radioactive ray, electron beam etc..
Ultraviolet light such as can by using high-pressure mercury-vapor lamp, melting H lamps, xenon lamp, black light lamp or LED light be used as ultraviolet light Source is irradiated.Electron beam can be irradiated by the ray of the generations such as electron-beam accelerator.
In the present invention, " energy ray-curable " refers to the property being cured by irradiation energy line, " non-energy line Curability " is even if refer to the property that irradiation energy line will not be cured.
《1st adhesive composition》
1st adhesive phase can be used the 1st adhesive composition containing adhesive and be formed.For example, by the 1st bonding The formation object surface of oxidant layer applies the 1st adhesive composition and makes it dry as needed, can be formed at the position of target 1st adhesive phase.For the more specifically forming method of the 1st adhesive phase, by the forming method later together with other layers It is described in detail together.The content ratio of the ingredient not gasified under room temperature in 1st adhesive composition to each other is led to The content ratio of the mentioned component of 1 adhesive phases of Chang Yu to each other is identical.It should be noted that in the present specification, " often Refer to not feel cold temperature " also athermic temperature, i.e. usual temperature, and it can be mentioned, for example 15~25 DEG C temperature etc..
The coating of 1st adhesive composition using well known method carry out, it can be mentioned, for example use Kohler coater, Scraper plate coating machine, bar coater, gravure coater, roll coater, roller knife coating machine, curtain stream coating machine, die coating machine, knife type coater, The method of the various coating machines such as silk screen coating machine, Meyer bar coater, kiss coater.
The drying condition of 1st adhesive composition is not particularly limited, but is contained in the 1st adhesive composition and described hereinafter Solvent in the case of, preferably it is thermally dried.For the 1st adhesive composition containing solvent, preferably with for example It is dried in the condition that 70~130 DEG C carry out 10 seconds~5 minutes.
In the case that 1st adhesive phase is energy ray-curable, as the 1st bonding containing energy ray-curable adhesive 1st adhesive composition of agent composition, i.e. energy ray-curable, it can be mentioned, for example：Bonding containing non-energy line curability 1st adhesive group of property resin (I-1a) (being also abbreviated as below " resin of binding property (I-1a) ") and energy ray-curable compound Close object (I-1)；Side chain containing the resin of binding property (I-1a) in non-energy line curability is imported with the energy of unsaturated group 1st adhesive composition of the resin of binding property (I-2a) (being also abbreviated as below " resin of binding property (I-2a) ") of line curability (I-2)；The 1st adhesive composition (I- containing above-mentioned resin of binding property (I-2a) and energy ray-curable low molecular compound 3) etc..
<1st adhesive composition (I-1)>
As described above, resin of binding property (I-1a) of above-mentioned 1st adhesive composition (I-1) containing non-energy line curability With energy ray-curable compound.
[resin of binding property (I-1a)]
Above-mentioned resin of binding property (I-1a) is preferably acrylic resin.
As above-mentioned acrylic resin, it can be mentioned, for example：At least there is the structure from (methyl) alkyl acrylate The acrylic polymer of unit.
Structural unit possessed by above-mentioned acrylic resin can be only a kind of or two or more, be two kinds In the case of above, combination thereof and ratio can be selected arbitrarily.
As above-mentioned (methyl) alkyl acrylate, it can be mentioned, for example the alkyl for forming Arrcostab carbon atom number for 1~ 20 (methyl) alkyl acrylate, abovementioned alkyl are preferably straight-chain or branched.
More specifically, it as (methyl) alkyl acrylate, can enumerate：(methyl) methyl acrylate, (methyl) propylene Acetoacetic ester, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) acrylic acid Isobutyl ester, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) acrylic acid oneself Ester, (methyl) heptylacrylate, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid are just Monooctyl ester, the positive nonyl ester of (methyl) acrylic acid, the different nonyl ester of (methyl) acrylic acid, (methyl) decyl acrylate, (methyl) acrylic acid 11 Arrcostab, (methyl) dodecylacrylate ((methyl) lauryl acrylate), (methyl) tridecyl acrylate, (first Base) acrylic acid tetradecane base ester ((methyl) myristyl ester), (methyl) acrylic acid pentadecane base ester, (methyl) acrylic acid Cetyl ester ((methyl) acrylic acid palm ester), (methyl) acrylic acid heptadecane base ester, (methyl) octadecyl acrylate ((methyl) stearyl acrylate), (methyl) acrylic acid nonadecane base ester, (methyl) acrylic acid eicosane base ester etc..
From the viewpoint of the bonding force for improving the 1st adhesive phase, above-mentioned acrylic polymer preferably has from upper The structural unit of (methyl) alkyl acrylate that the carbon atom number for stating alkyl is more than 4.Wherein, from can further improve the 1st From the perspective of the bonding force of adhesive phase, the carbon atom number of abovementioned alkyl is preferably 4~12, more preferably 4~8.On in addition, (methyl) alkyl acrylate that the carbon atom number for stating alkyl is more than 4 is preferably alkyl acrylate.
Above-mentioned acrylic polymer is preferably other than being originated from the structural unit of (methyl) alkyl acrylate, further With the structural unit from the monomer containing functional group.
As the above-mentioned monomer containing functional group, it can be mentioned, for example：Above-mentioned functional group with crosslinking agent described later by sending out Raw reaction and can become crosslinked starting point or above-mentioned functional group by with the unsaturated group in the compound containing unsaturated group Group reacts and can be imported in the side chain of acrylic polymer the compound of unsaturated group.
As the above-mentioned functional group in the monomer containing functional group, it can be mentioned, for example：Hydroxyl, carboxyl, amino, epoxy group etc..
That is, as the monomer containing functional group, it can be mentioned, for example：Hydroxyl monomer, emulsion stability, contains carboxyl group-containing monomer Epoxy based monomers etc..
As above-mentioned hydroxyl monomer, it can be mentioned, for example：(methyl) dihydroxypropyl methyl esters, (methyl) acrylic acid 2- hydroxyls Ethyl ester, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 3- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxybutyls, (first Base) (methyl) hydroxyalkyl acrylates such as acrylic acid 3- hydroxybutyls, (methyl) acrylic acid 4- hydroxybutyls；Vinyl alcohol, alkene Non- (methyl) acrylic compounds unsaturated alcohol such as propyl alcohol (unsaturated alcohol for not having (methyl) acryloyl group skeleton) etc..
As above-mentioned carboxyl group-containing monomer, it can be mentioned, for example：The olefinics unsaturated monocarboxylic acids such as (methyl) acrylic acid, crotonic acid (monocarboxylic acid with ethylenic unsaturated bond)；The olefinics unsaturated dicarboxylic acid such as fumaric acid, itaconic acid, maleic acid, citraconic acid (dicarboxylic acids with ethylenic unsaturated bond)；The acid anhydrides of above-mentioned olefinic unsaturated dicarboxylic acid；Methacrylic acid 2- carboxyl second Ester etc. (methyl) acrylic acid carboxyalkyl ester etc..
Monomer containing functional group is preferably hydroxyl monomer, carboxyl group-containing monomer, more preferably hydroxyl monomer.
The monomer containing functional group for forming above-mentioned acrylic polymer can be only a kind of or two or more, In the case of two or more, combination thereof and ratio can be selected arbitrarily.
In above-mentioned acrylic polymer, relative to the total amount of structural unit, the structure from the monomer containing functional group The content of unit is preferably 1~35 mass %, more preferably 3~32 mass %, particularly preferably 5~30 mass %.
In addition to being originated from the structural unit of (methyl) alkyl acrylate and from containing function in above-mentioned acrylic polymer Other than the structural unit of the monomer of group, can also further have the structural unit from other monomers.
As long as above-mentioned other monomers can be then not particularly limited with the monomer of the copolymerization such as (methyl) alkyl acrylate.
As above-mentioned other monomers, it can be mentioned, for example：Styrene, α-methylstyrene, vinyltoluene, vinyl formate Ester, vinyl acetate, acrylonitrile, acrylamide etc..
It can be only a kind of or two or more to form above-mentioned other monomers of above-mentioned acrylic polymer, be In the case of two or more, combination thereof and ratio can be selected arbitrarily.
Resin of binding property (I-1a) of the above-mentioned acrylic polymer as above-mentioned non-energy line curability can be used.
On the other hand, as the resin of binding property (I-2a) of above-mentioned energy ray-curable, can use make with energy The compound containing unsaturated group of line polymerism unsaturated group (energy line polymerizable group) and above-mentioned acrylic The polymer that functional group reactions in object form.
It should be noted that in the present invention, " energy line polymerism " refers to what is polymerize by irradiation energy line Property.
The resin of binding property (I-1a) contained in 1st adhesive composition (I-1) can be only one kind or two kinds More than, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
In the 1st adhesive composition (I-1), the content of resin of binding property (I-1a) is preferably 5~99 mass %, more excellent It is selected as 10~95 mass %, particularly preferably 15~90 mass %.
[energy ray-curable compound]
As the above-mentioned energy ray-curable compound contained in the 1st adhesive composition (I-1), can enumerate：With energy Measure line polymerism unsaturated group, the monomer or oligomer that can be cured by irradiation energy line.
As the monomer in energy ray-curable compound, it can be mentioned, for example：Trimethylolpropane tris (methyl) acrylic acid Ester, pentaerythrite (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylic acid Polynary (methyl) acrylate such as ester, 1,4- butanediols two (methyl) acrylate, 1,6-HD (methyl) acrylate；Ammonia Carbamate (methyl) acrylate；Polyester (methyl) acrylate；Polyethers (methyl) acrylate；Epoxy (methyl) acrylic acid Ester etc..
As the oligomer in energy ray-curable compound, it can be mentioned, for example：The monomer that above-mentioned middle example goes out is aggregated Oligomer formed etc..
From the viewpoint of molecular weight it is larger, do not easily lead to the 1st adhesive phase storage modulus reduce, energy ray-curable Compound is preferably carbamate (methyl) acrylate, carbamate (methyl) acrylate oligomer.
The above-mentioned energy ray-curable compound contained in 1st adhesive composition (I-1) can be only one kind, can also It is two or more, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
In above-mentioned 1st adhesive composition (I-1), the content of above-mentioned energy ray-curable compound is preferably 1~95 Quality %, more preferably 5~90 mass %, particularly preferably 10~85 mass %.
[crosslinking agent]
As resin of binding property (I-1a), using in addition to the structural unit from (methyl) alkyl acrylate In the case of the above-mentioned acrylic polymer further with the structural unit from the monomer containing functional group, the 1st adhesive Preferably further contain crosslinking agent in composition (I-1).
Above-mentioned crosslinking agent is for example with above-mentioned functional group reactions and by resin of binding property (I-1a) crosslinked ingredient to each other.
As crosslinking agent, it can be mentioned, for example：Toluene di-isocyanate(TDI), hexamethylene diisocyanate, phenylenedimethylidyne two The isocyanates crosslinking agent such as adduct (crosslinking agent with isocyanate group) of isocyanates, these diisocyanate；Second The epoxies such as glycol glycidyl ether crosslinking agent (crosslinking agent with glycidyl)；Six [1- (2- methyl) '-aziridinos] The aziridines crosslinking agents such as three phospha triazines (crosslinking agent with '-aziridino)；The metal-chelatings species crosslinking agent such as aluminium chelate compound (crosslinking agent with metallo-chelate structure)；Isocyanuric acid esters crosslinking agent (crosslinking agent with isocyanuric acid skeleton) etc..
From the cohesiveness raising of adhesive is made so as to improve the viewpoint of the bonding force of the 1st adhesive phase and easily acquisition etc. Viewpoint is set out, and crosslinking agent is preferably isocyanates crosslinking agent.
The crosslinking agent contained in 1st adhesive composition (I-1) can be only a kind of or two or more, be two Kind or more in the case of, combination thereof and ratio can be selected arbitrarily.
In above-mentioned 1st adhesive composition (I-1), relative to 100 mass parts of content of resin of binding property (I-1a), hand over The content of connection agent is preferably 0.01~50 mass parts, particularly preferably more preferably 0.1~20 mass parts, 1~10 mass parts.
[Photoepolymerizationinitiater initiater]
1st adhesive composition (I-1) can also further contain Photoepolymerizationinitiater initiater.Just containing Photoepolymerizationinitiater initiater For 1st adhesive composition (I-1), even if having irradiated the energy line compared with low energy such as ultraviolet light, curing reaction can also fill Ground is divided to carry out.
As above-mentioned Photoepolymerizationinitiater initiater, it can be mentioned, for example：Benzoin, benzoin methyl ether, benzoin ethyl ether, benzene are even The benzene such as relation by marriage isopropyl ether, benzoin isobutyl ether, benzoin benzoic acid, benzoin methyl benzoate, benzil dimethyl ketal are even Relation by marriage compound；Acetophenone, 2- hydroxy-2-methyl -1- phenyl-propan -1- ketone, 2,2- dimethoxy -1,2- diphenylethanes -1- The acetophenone compounds such as ketone；Bis- (2,4,6- trimethylbenzoyls) phenyl phosphine oxides, 2,4,6- trimethyl benzoyl diphenyls The acylphosphine oxide compounds such as base phosphine oxide；The sulfide compounds such as benzyl phenyl thioether, tetra methylthiuram list sulfide；1- hydroxyls The α -one alcoholic compounds such as butylcyclohexyl phenyl ketone；The azo-compounds such as azodiisobutyronitrile；The titanocenes compound such as titanocenes；Thiophene The thioxanthone compounds such as ton ketone；Peroxide compound；The dione compounds such as diacetyl；Dibenzoyl；Bibenzyl；Benzophenone；2, 4- diethyl thioxanthones；1,2- diphenyl methanes；2- hydroxy-2-methyls -1- [4- (1- methyl ethylenes) phenyl] acetone；2- chlorine Anthraquinone etc..
In addition, as above-mentioned Photoepolymerizationinitiater initiater, can also use for example：The naphtoquinone compounds such as 1- chloroanthraquinones；Amine etc. is photosensitive Agent etc..
The Photoepolymerizationinitiater initiater contained in 1st adhesive composition (I-1) can be only a kind of or two kinds with On, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
In the 1st adhesive composition (I-1), relative to 100 mass parts of content of above-mentioned energy ray-curable compound, The content of Photoepolymerizationinitiater initiater is preferably 0.01~20 mass parts, more preferably 0.03~10 mass parts, particularly preferably 0.05 ~5 mass parts.
[other additives]
1st adhesive composition (I-1) can also in the range of effect of the present invention is not destroyed containing be not belonging to it is above-mentioned in Any ingredient other additives.
As above-mentioned other additives, it can be mentioned, for example：Antistatic agent, antioxidant, softening agent (plasticizer), packing material (filler), antirust agent, colorant (pigment, dyestuff), sensitizer, tackifier, reaction suppressor, crosslinking accelerator (catalyst) etc. Well known additive.
It should be noted that reaction suppressor refers to inhibit such as urging in the 1st adhesive composition (I-1) is mixed into The additive of non-targeted cross-linking reaction occurs in the 1st adhesive composition (I-1) under the action of agent in preservation.As Reaction suppressor, it can be mentioned, for example：The substance of chelate complexes is formed by being chelated with catalyst, more specifically, can be arranged Lifting has the reaction suppressor of 2 or more carbonyls (- C (=O) -) in 1 molecule.
The other additives contained in 1st adhesive composition (I-1) can be only a kind of or two or more, In the case of two or more, combination thereof and ratio can be selected arbitrarily.
In the 1st adhesive composition (I-1), the content of other additives is not particularly limited, appropriate according to its type Selection.
[solvent]
Solvent can also be contained in 1st adhesive composition (I-1).1st adhesive composition (I-1) is molten by containing Agent is improved relative to the coating adaptability of coating object surface.
Above-mentioned solvent is preferably organic solvent, as above-mentioned organic solvent, it can be mentioned, for example：The ketone such as methyl ethyl ketone, acetone；Second The esters such as acetoacetic ester (carboxylate)；Tetrahydrofuran, twoThe ethers such as alkane；The aliphatic hydrocarbons such as hexamethylene, n-hexane；The virtues such as toluene, dimethylbenzene Fragrant hydrocarbon；Alcohol such as 1- propyl alcohol, 2- propyl alcohol etc..
As above-mentioned solvent, such as can not also be by the solvent used when manufacturing resin of binding property (I-1a) from adhesiveness It removes in resin (I-1a), but is directly used in the 1st adhesive composition (I-1).Alternatively, as above-mentioned solvent, also may be used With the solvent used when in addition added when manufacturing the 1st adhesive composition (I-1) in the manufacture of resin of binding property (I-1a) Identical type or different kinds of liquid solvents.
The solvent contained in 1st adhesive composition (I-1) can be only a kind of or two or more.1st bonding In the case that the solvent contained in agent composition (I-1) is two or more, combination thereof and ratio can be selected arbitrarily.
In the 1st adhesive composition (I-1), the content of solvent is not particularly limited, appropriate to adjust.
<1st adhesive composition (I-2)>
As described above, contain the resin of binding property in non-energy line curability in above-mentioned 1st adhesive composition (I-2) (I-1a) side chain is imported with the resin of binding property (I-2a) of the energy ray-curable of unsaturated group.
[resin of binding property (I-2a)]
Above-mentioned resin of binding property (I-2a) for example can by make to have energy line polymerism unsaturated group containing unsaturation The compound of group is obtained with the functional group reactions in resin of binding property (I-1a).
The above-mentioned compound containing unsaturated group be other than with above-mentioned energy line polymerism unsaturated group also into One step has can be by the group that is combined with the functional group reactions in resin of binding property (I-1a) with resin of binding property (I-1a) Compound.
As above-mentioned energy line polymerism unsaturated group, it can be mentioned, for example：(methyl) acryloyl group, vinyl (vinyl Group, ethenyl group), pi-allyl (2- acrylic) etc., preferably (methyl) acryloyl group.
As can with the group of the functional groups in resin of binding property (I-1a), it can be mentioned, for example：It can be with hydroxyl Or the isocyanate group and glycidyl and the hydroxyl that can be combined with carboxyl or epoxy group and amino etc. of amino combination.
As the above-mentioned compound containing unsaturated group, it can be mentioned, for example：(methyl) acryloyloxyethyl isocyanate, (methyl) acryloyl isocyanates, (methyl) glycidyl acrylate etc..
The resin of binding property (I-2a) contained in 1st adhesive composition (I-2) can be only one kind or two kinds More than, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
In the 1st adhesive composition (I-2), the content of resin of binding property (I-2a) is preferably 5~99 mass %, more excellent It is selected as 10~95 mass %, particularly preferably 10~90 mass %.
[crosslinking agent]
As resin of binding property (I-2a), it is originated from using have identical in resin of binding property (I-1a) containing function It can also be into the case of the above-mentioned acrylic polymer of the structural unit of the monomer of group, in the 1st adhesive composition (I-2) One step contains crosslinking agent.
As the above-mentioned crosslinking agent in the 1st adhesive composition (I-2), can enumerate in the 1st adhesive composition (I-1) Identical those of crosslinking agent.
The crosslinking agent contained in 1st adhesive composition (I-2) can be only a kind of or two or more, be two Kind or more in the case of, combination thereof and ratio can be selected arbitrarily.
In above-mentioned 1st adhesive composition (I-2), relative to 100 mass parts of content of resin of binding property (I-2a), hand over The content of connection agent is preferably 0.01~50 mass parts, particularly preferably more preferably 0.1~20 mass parts, 1~10 mass parts.
[Photoepolymerizationinitiater initiater]
It can also further contain Photoepolymerizationinitiater initiater in 1st adhesive composition (I-2).Cause for containing photopolymerization 1st adhesive composition (I-2) of agent, even if having irradiated the energy line compared with low energy such as ultraviolet light, curing reaction can also fill Ground is divided to carry out.
As the above-mentioned Photoepolymerizationinitiater initiater in the 1st adhesive composition (I-2), can enumerate and the 1st adhesive composition (I-1) identical those of Photoepolymerizationinitiater initiater in.
The Photoepolymerizationinitiater initiater contained in 1st adhesive composition (I-2) can be only a kind of or two kinds with On, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
In the 1st adhesive composition (I-2), relative to 100 mass parts of content of resin of binding property (I-2a), photopolymerization The content of initiator is preferably 0.01~20 mass parts, particularly preferably more preferably 0.03~10 mass parts, 0.05~5 mass Part.
[other additives]
1st adhesive composition (I-2) can also in the range of effect of the present invention is not destroyed containing be not belonging to it is above-mentioned in Any ingredient other additives.
As above-mentioned other additives in the 1st adhesive composition (I-2), can enumerate and the 1st adhesive composition (I- 1) identical those of other additives in.
The other additives contained in 1st adhesive composition (I-2) can be only a kind of or two or more, In the case of two or more, combination thereof and ratio can be selected arbitrarily.
In the 1st adhesive composition (I-2), the content of other additives is not particularly limited, appropriate according to its type Selection.
[solvent]
For the same purpose of situation with the 1st adhesive composition (I-1), in the 1st adhesive composition (I-2) Solvent can be contained.
As the above-mentioned solvent in the 1st adhesive composition (I-2), can enumerate in the 1st adhesive composition (I-1) Identical those of solvent.
The solvent contained in 1st adhesive composition (I-2) can be only a kind of or two or more, be two kinds In the case of above, combination thereof and ratio can be selected arbitrarily.
In the 1st adhesive composition (I-2), the content of solvent is not particularly limited, appropriate to adjust.
<1st adhesive composition (I-3)>
As described above, above-mentioned 1st adhesive composition (I-3) is consolidated containing above-mentioned resin of binding property (I-2a) and energy line The property changed low molecular compound.
In the 1st adhesive composition (I-3), the content of resin of binding property (I-2a) is preferably 5~99 mass %, more excellent It is selected as 10~95 mass %, particularly preferably 15~90 mass %.
[energy ray-curable low molecular compound]
As the above-mentioned energy ray-curable low molecular compound contained in the 1st adhesive composition (I-3), energy can be enumerated Line polymerism unsaturated group, the monomer and oligomer that can be cured by irradiation energy line are measured, can enumerate and be glued with the 1st Identical those of the energy ray-curable compound that contains in mixture composite (I-1).
The above-mentioned energy ray-curable low molecular compound contained in 1st adhesive composition (I-3) can be only one kind, Can also be two or more, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
In above-mentioned 1st adhesive composition (I-3), relative to 100 mass parts of content of resin of binding property (I-2a), on The content for stating energy ray-curable low molecular compound is preferably 0.01~300 mass parts, more preferably 0.03~200 mass Part, particularly preferably 0.05~100 mass parts.
[Photoepolymerizationinitiater initiater]
1st adhesive composition (I-3) can also further contain Photoepolymerizationinitiater initiater.For containing Photoepolymerizationinitiater initiater The 1st adhesive composition (I-3), even if having irradiated the energy line compared with low energy such as ultraviolet light, curing reaction also can be abundant Ground carries out.
As the above-mentioned Photoepolymerizationinitiater initiater in the 1st adhesive composition (I-3), can enumerate and the 1st adhesive composition (I-1) identical those of Photoepolymerizationinitiater initiater in.
The Photoepolymerizationinitiater initiater contained in 1st adhesive composition (I-3) can be only a kind of or two kinds with On, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
In the 1st adhesive composition (I-3), relative to resin of binding property (I-2a) and low point of above-mentioned energy ray-curable 100 mass parts of total content of sub- compound, the content of Photoepolymerizationinitiater initiater is preferably 0.01~20 mass parts, more preferably 0.03 ~10 mass parts, particularly preferably 0.05~5 mass parts.
[other additives]
1st adhesive composition (I-3) can also in the range of effect of the present invention is not destroyed containing be not belonging to it is above-mentioned in Any ingredient other additives.
As above-mentioned other additives, that identical with other additives in the 1st adhesive composition (I-1) can be enumerated A bit.
The other additives contained in 1st adhesive composition (I-3) can be only a kind of or two or more, In the case of two or more, combination thereof and ratio can be selected arbitrarily.
In the 1st adhesive composition (I-3), the content of other additives is not particularly limited, appropriate according to its type Selection.
[solvent]
For the same purpose of situation with the 1st adhesive composition (I-1), also may be used in the 1st adhesive composition (I-3) To contain solvent.
As the above-mentioned solvent in the 1st adhesive composition (I-3), can enumerate in the 1st adhesive composition (I-1) Identical those of solvent.
The solvent contained in 1st adhesive composition (I-3) can be only a kind of or two or more, be two kinds In the case of above, combination thereof and ratio can be selected arbitrarily.
In the 1st adhesive composition (I-3), the content of solvent is not particularly limited, appropriate to adjust.
<The 1st adhesive composition other than 1st adhesive composition (I-1)~(I-3)>
Here, it is combined mainly for the 1st adhesive composition (I-1), the 1st adhesive composition (I-2) and the 1st adhesive Object (I-3) is illustrated, but other than this 3 kind of the 1st adhesive composition universal the 1st adhesive composition ( In in this specification, referred to as " the 1st adhesive composition other than the 1st adhesive composition (I-1)~(I-3) "), as these Composition can similarly be used containing the ingredient illustrated by ingredient.
As the 1st adhesive composition other than the 1st adhesive composition (I-1)~(I-3), in addition to energy ray-curable Adhesive composition other than, can also enumerate the adhesive composition of non-energy line curability.
As the adhesive composition of non-energy line curability, it can be mentioned, for example (have (first containing acrylic resin Base) acryloyl group resin), urethane based resin (resin with amino-formate bond), rubber resin is (with rubber The resin of plastic structure), organic silicon resin (resin with siloxanes key), epoxylite (resin with epoxy group), The composition of the resin of binding property such as polyvingl ether or makrolon, the preferably composition containing acrylic resin.
The 1st adhesive composition other than 1st adhesive composition (I-1)~(I-3) preferably comprise it is one or two kinds of with On crosslinking agent, content can be identical with the situation of the 1st above-mentioned adhesive composition (I-1) etc..
《The manufacturing method of 1st adhesive composition》
Above-mentioned 1st adhesive compositions such as the 1st adhesive composition (I-1)~(I-3) can by coordinate above-mentioned adhesive, With as needed and using ingredient other than above-mentioned adhesive etc. for form the 1st adhesive composition each ingredient and obtain.
Order of addition during each ingredient is coordinated to be not particularly limited, two or more ingredients can also be added simultaneously.
In the case of using solvent, this can be matched by being mixed with the arbitrary gradation composition in addition to solvent solvent Synthesis divide beforehand dilution after use, the arbitrary gradation composition other than solvent can not also be diluted in advance, but pass through by Solvent is mixed with these gradation compositions and is used.
For the method that each ingredient mixes is not particularly limited during cooperation, from rotate stirrer or agitating paddle etc. and into The method of row mixing, using method that mixer is mixed, apply in method well known to method that ultrasonic wave mixed etc. Appropriate selection.
The temperature and time when addition and mixing of each ingredient is not as long as long as causing in the case of each gradation composition deterioration It is not particularly limited, it is appropriate to adjust, but preferable temperature is 15~30 DEG C.
0 the 1st middle layer
Above-mentioned 1st middle layer is sheet or membranaceous, and constituent material is suitably selected according to purpose, without special limit It is fixed.
For example, with by the way that the protective film of covering semiconductor surface is made to reflect the shape for the convex block for being present in semiconductor surface Shape so as to inhibit protective film deform for the purpose of in the case of, as the preferred constituent material of above-mentioned 1st middle layer, from into From the perspective of one step improves the stickup of the 1st middle layer, carbamate (methyl) acrylate etc. can be enumerated.
1st middle layer can be only one layer (individual layer) or more than two layers of multilayer, should in the case of being multilayer Multilayer mutually can be the same or different, and the combination of the multilayer is not particularly limited.
The thickness of 1st middle layer can suitably be adjusted according to the height of the convex block of the semiconductor surface as protection object, But from the viewpoint of also can easily absorbing the influence for higher-height convex block, preferably 50~600 μm, more preferably It is 70~500 μm, particularly preferably 80~400 μm.
Here, described " thickness of the 1st middle layer " represents the thickness of the 1st middle layer entirety, for example, be made up of multiple layers the The thickness of 1 middle layer refers to form the aggregate thickness of whole layers of the 1st middle layer.
《1st middle layer formation composition》
1st middle layer can be used the 1st middle layer formation composition containing its constituent material and be formed.For example, pass through The 1st middle layer formation composition is applied in the formation object surface of the 1st middle layer and is made it dry as needed or is passed through photograph It penetrates energy line and makes its curing, the 1st middle layer can be formed at the position of target.For the more specifically shape of the 1st middle layer Into method, will be described in detail later together with other layers of forming method.In 1st middle layer formation composition Content ratio of the content ratio of the ingredient not gasified under room temperature to each other usually with the mentioned component of the 1st middle layer to each other Rate is identical.Here, described " room temperature " as mentioned before.
The coating that 1st middle layer forms composition is carried out using well known method, and it can be mentioned, for example use air knife Coating machine, scraper plate coating machine, bar coater, gravure coater, roll coater, roller knife coating machine, curtain stream coating machine, die coating machine, scraper The method of the various coating machines such as coating machine, silk screen coating machine, Meyer bar coater, kiss coater.
The drying condition of 1st middle layer formation composition is not particularly limited.It is such as described later molten for containing 1st middle layer formation composition of agent, is preferably thermally dried, at this point, it is preferred that for example to be carried out 10 seconds in 70~130 DEG C The condition of clock~5 minute is dried.
In the case where the 1st middle layer formation has energy ray-curable with composition, preferably further lead to after the drying It crosses irradiation energy line and makes its curing.
As the 1st middle layer formation composition, it can be mentioned, for example：Containing carbamate (methyl) acrylate 1 middle layer is formed with composition (II-1) etc..
<1st middle layer is formed with composition (II-1)>
As described above, the 1st middle layer is formed contains carbamate (methyl) acrylate with composition (II-1).
[carbamate (methyl) acrylate]
Carbamate (methyl) acrylate is that at least have (methyl) acryloyl group and carbamate in 1 molecule The compound of key, with energy line polymerism.
Carbamate (methyl) acrylate either carbamate (methyl) acrylate of simple function (1 Only there is carbamate (methyl) acrylate of 1 (methyl) acryloyl group in molecule) or difunctionality more than Carbamate (methyl) acrylate (has the carbamate (methyl) of 2 or more (methyl) acryloyl groups in 1 molecule Acrylate), i.e. polyfunctional carbamate (methyl) acrylate.But in the present invention, as carbamate (first Base) acrylate, preferably at least using the carbamate of simple function (methyl) acrylate.
As above-mentioned carbamate (methyl) acrylate contained in the 1st middle layer formation composition, can enumerate Such as：Make by polyol compound and polyisocyanate compound terminal isocyanate carbamate prepolymer obtained by the reaction Carbamate obtained from further being reacted with (methyl) acrylic compounds with hydroxyl and (methyl) acryloyl group (methyl) acrylate.Here, " terminal isocyanate carbamate prepolymer " refers to, with amino-formate bond, simultaneously There is the prepolymer of isocyanate group in molecular end portion.
Carbamate (methyl) acrylate contained in 1st middle layer formation composition (II-1) can be only one It plants or two or more, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
(polyol compound)
As long as above-mentioned polyol compound compound with 2 or more hydroxyls in 1 molecule is then not particularly limited.
Above-mentioned polyol compound can be used alone, and can also be used in combination of two or more, be applied in combination two Kind or more in the case of, combination thereof and ratio can be selected arbitrarily.
As above-mentioned polyol compound, it can be mentioned, for example：Aklylene glycol, polyether polyol, polyester polyol, Polycarbonate polyol etc..
Above-mentioned polyol compound can be more than the dihydric alcohol, the trihydroxylic alcohol of trifunctional, tetrafunctional of difunctionality polynary Any compound in alcohol etc. obtains, from the viewpoint of easy versatility and reactivity etc. are excellent, preferably dihydric alcohol.
Polyether polyol
Above-mentioned polyether polyol is not particularly limited, but preferably polyether-type dihydric alcohol, as above-mentioned polyether-type binary Alcohol, it can be mentioned, for example the following general formula (1) compounds represented.
[chemical formula 1]
(in formula, n is more than 2 integer；R is divalent alkyl, and multiple R mutually can be the same or different.)
In formula, n represents the number of repeat unit of the group shown in general formula "-R-O- ", as long as more than 2 integer is then without spy It is different to limit.Wherein, n is preferably 10~250, more preferably 25~205, particularly preferably 40~185.
In formula, R is not particularly limited, but preferably alkylidene as long as divalent alkyl, more preferably carbon atom number 1~6 Alkylidene, further preferably ethylidene, propylidene or tetramethylene, particularly preferably propylidene or tetramethylene.
Above-mentioned formula (1) compound represented is preferably polyethylene glycol, polypropylene glycol or polytetramethylene glycol, more preferably Polypropylene glycol or polytetramethylene glycol.
By reacting above-mentioned polyether-type dihydric alcohol and above-mentioned polyisocyanate compound, as above-mentioned end isocyanates Carbamate prepolymer can obtain the prepolymer with the ehter bond portion shown in the following general formula (1a).And then by using above-mentioned Such terminal isocyanate carbamate prepolymer, above-mentioned carbamate (methyl) acrylate, which becomes, has above-mentioned ether Carbamate (methyl) acrylate in key portion has the amino first of the structural unit as derived from above-mentioned polyether-type dihydric alcohol Acid esters (methyl) acrylate.
[chemical formula 2]
(in formula, R and n are same as described above.)
Polyester polyol
Above-mentioned polyester polyol is not particularly limited, and it can be mentioned, for example carry out ester by using polyacid or derivatives thereof Polyalcohol obtained from changing reaction.It should be noted that " derivative " in this specification, in the feelings of no specified otherwise Under condition, the compound that 1 or more group of former compound is formed by group (substituent group) substitution in addition to it is represented.Here, " group " does not only include the atomic group formed by multiple atomistic bindings, further includes 1 atom.
As above-mentioned polyacid and its derivative, the polyacid for the manufacture raw material for being often used as polyester can be enumerated and its spread out Biology.
As above-mentioned polyacid, it can be mentioned, for example：Representative examples of saturated aliphatic polyacid, unsaturated aliphatic polyacid, aromatic series Polyacid etc. can also use dimeric dibasic acid corresponding with the arbitrary polyacid in these.
As above-mentioned representative examples of saturated aliphatic polyacid, it can be mentioned, for example：Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, Representative examples of saturated aliphatic binary acid such as pimelic acid, suberic acid, azelaic acid, decanedioic acid etc..
As above-mentioned unsaturated aliphatic polyacid, it can be mentioned, for example：The unsaturated aliphatics binary such as maleic acid, fumaric acid Acid etc..
It is sour as above-mentioned aromatic polyvalent, it can be mentioned, for example：Phthalic acid, M-phthalic acid, terephthalic acid (TPA), 2,6- The aromatic acids such as naphthalenedicarboxylic acid；The aromatic series ternary acid such as trimellitic acid；Aromatic series tetra-atomic acid such as Pyromellitic Acid etc..
As the derivative of above-mentioned polyacid, it can be mentioned, for example：Above-mentioned representative examples of saturated aliphatic polyacid, unsaturated aliphatic Acid anhydrides and hydrogenated dimer acids of polyacid and aromatic polyvalent acid etc..
Above-mentioned polyacid or derivatives thereof both can be used alone, and can also be used in combination of two or more, will In the case of being used in combination, combination thereof and ratio can be selected arbitrarily.
From the viewpoint of being suitably formed the film with appropriate hardness, above-mentioned polyacid is preferably aromatic polyvalent acid.
In the esterification for obtaining polyester polyol, well known catalyst can also be used as needed.
As above-mentioned catalyst, it can be mentioned, for example：The tin compounds such as Dibutyltin oxide, stannous octoate；Butyl titanate, Alkoxytitaniums such as metatitanic acid orthocarbonate etc..
Polycarbonate polyol
Polycarbonate polyol is not particularly limited, identical with above-mentioned formula (1) compound represented it can be mentioned, for example making Glycol and alkylene carbonates reaction obtained from polyalcohol etc..
Here, glycol and alkylene carbonates both can be used alone, and can also be used in combination of two or more, In the case of being used in combination of two or more, combination thereof and ratio can be selected arbitrarily.
The number-average molecular weight calculated by the hydroxyl value of above-mentioned polyol compound is preferably 1000~10000, is more preferably 2000~9000,3000~7000 are particularly preferably.By the way that above-mentioned number-average molecular weight is made to be more than 1000, carbamic acid can inhibit The excessive generation of ester bond, so as to which the control for making the viscoelastic property of the 1st middle layer becomes more easy.It is in addition, above-mentioned by making Number-average molecular weight is for 10000 hereinafter, can inhibit overbating for the 1st middle layer.
It is the value calculated by following formula by the above-mentioned number-average molecular weight that the hydroxyl value of polyol compound calculates.
[number-average molecular weight of polyol compound]=[functional group number of polyol compound] × 56.11 × 1000/ are [more Hydroxyl value (the unit of first alcoholic compound：mgKOH/g)]
Above-mentioned polyol compound is preferably polyether polyol, more preferably polyether-type dihydric alcohol.
(polyisocyanate compound)
As long as the above-mentioned polyisocyanate compound reacted with polyol compound is with 2 or more isocyanate group Compound is then not particularly limited.
Polyisocyanate compound can be used alone, and can also be used in combination of two or more, will be two or more In the case of being applied in combination, combination thereof and ratio can be selected arbitrarily.
As above-mentioned polyisocyanate compound, it can be mentioned, for example：Tetramethylene diisocyanate, two isocyanide of hexa-methylene The chain fatties (cyclo) aliphatic diisocyanates such as acid esters, trimethyl hexamethylene diisocyanate；Isophorone diisocyanate, norborneol Alkane diisocyanate, dicyclohexyl methyl hydride -4,4 '-diisocyanate, dicyclohexyl methyl hydride -2,4 '-diisocyanate, ω, The ring-shaped fats (cyclo) aliphatic diisocyanates such as ω '-diisocyanate dimethyl cyclohexane；4,4 '-methyl diphenylene diisocyanate, first Phenylene diisocyanate, benzene dimethylene diisocyanate, dimethyl diphenyl diisocyanate, tetramethylene phenylenedimethylidyne two are different Aromatic diisocyanates such as cyanate, naphthalene -1,5- diisocyanate etc..
In these, from the aspect of operability, polyisocyanate compound is preferably isophorone diisocyanate, six Asias Methyl diisocyanate or benzene dimethylene diisocyanate.
((methyl) acrylic compounds)
Above-mentioned (methyl) reacted with above-mentioned end isocyanates carbamate prepolymer is as long as acrylic compounds It is that the compound at least having hydroxyl and (methyl) acryloyl group in 1 molecule is then not particularly limited.
Above-mentioned (methyl) acrylic compounds can be used alone, and can also be used in combination of two or more, will In the case of being used in combination, combination thereof and ratio can be selected arbitrarily.
As above-mentioned (methyl) acrylic compounds, it can be mentioned, for example：(methyl) acrylic acid 2- hydroxy methacrylates, (methyl) Acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 3- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxybutyls, (methyl) acrylic acid 3- Hydroxybutyl, (methyl) acrylic acid 4- hydroxybutyls, (methyl) acrylic acid 4- hydroxycyclohexyls, (methyl) acrylic acid 5- hydroxyl rings Monooctyl ester, (methyl) acrylic acid 2- hydroxyl -3- phenoxy-propyls, pentaerythrite three (methyl) acrylate, polyethyleneglycol (first Base) hydroxyls such as acrylate, (methyl) acrylic acid 2- hydroxy methacrylates (methyl) acrylate；N- methylols (methyl) third (methyl) acrylamide of the hydroxyls such as acrylamide；Make vinyl alcohol, vinylphenol or bisphenol A diglycidyl ether and (methyl) Reactant etc. obtained from acrylic acid reaction.
In these, above-mentioned (methyl) acrylic compounds are preferably (methyl) acrylate of hydroxyl, are more preferably (methyl) alkyl acrylate of hydroxyl, particularly preferably (methyl) acrylic acid 2- hydroxy methacrylates.
Above-mentioned end isocyanates carbamate prepolymer also may be used with above-mentioned reacting for (methyl) acrylic compounds To use the progress such as solvent, catalyst as needed.
For reacting above-mentioned end isocyanates carbamate prepolymer and above-mentioned (methyl) acrylic compounds When condition, carry out suitably adjust, for example, reaction temperature is preferably 60~100 DEG C, the reaction time is preferably 1~4 small When.
Above-mentioned carbamate (methyl) acrylate can be oligomer, polymer and oligomer and polymer Arbitrary situation in mixture, preferably oligomer.
For example, the weight average molecular weight of above-mentioned carbamate (methyl) acrylate be preferably 1000~100000, it is more excellent It is selected as 3000~80000, particularly preferably 5000~65000.By the way that above-mentioned weight average molecular weight is made to be more than 1000, in amino first In the polymer that acid esters (methyl) acrylate is formed with polymerizable monomer described later, based on from carbamate (first Base) acrylate structure molecular separating force to each other, easily make being optimal of hardness of the 1st middle layer.
It should be noted that in the present specification, in the case of no specified otherwise, weight average molecular weight is to utilize gel The polystyrene scaled value that permeation chromatography (GPC) method measures.
[polymerizable monomer]
From the viewpoint of being further improved film forming, the 1st middle layer, which is formed, to be used in composition (II-1) in addition to above-mentioned ammonia It can also contain polymerizable monomer other than carbamate (methyl) acrylate.
Above-mentioned polymerizable monomer be preferably with energy line polymerism, except weight average molecular weight be more than 1000 oligomer and The compound in 1 molecule at least one (methyl) acryloyl group other than polymer.
As above-mentioned polymerizable monomer, it can be mentioned, for example：The alkyl for forming Arrcostab is the chain that carbon atom number is 1~30 (methyl) alkyl acrylate of alkyl；(the first containing functional group with functional groups such as hydroxyl, amide groups, amino or epoxy groups Base) acrylic compounds；(methyl) acrylate with aliphatic ring type group；(methyl) third with aromatic hydrocarbyl Olefin(e) acid ester；(methyl) acrylate with hetero ring type group；Compound with vinyl；Compound with pi-allyl Deng.
As with carbon atom number be 1~30 chain-like alkyl above-mentioned (methyl) alkyl acrylate, it can be mentioned, for example： (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (first Base) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (first Base) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) n-octyl, (methyl) propylene The different monooctyl ester of acid, (methyl) 2-EHA, the positive nonyl ester of (methyl) acrylic acid, the different nonyl ester of (methyl) acrylic acid, (methyl) Decyl acrylate, (methyl) acrylic acid hendecane base ester, (methyl) dodecylacrylate ((methyl) lauryl acrylate), (methyl) tridecyl acrylate, (methyl) acrylic acid tetradecane base ester ((methyl) myristyl ester), (methyl) third Olefin(e) acid pentadecane base ester, (methyl) aliphatic acrylate ((methyl) acrylic acid palm ester), (methyl) acrylic acid heptadecane Base ester, (methyl) octadecyl acrylate ((methyl) stearyl acrylate), (methyl) acrylic acid isooctadecane base ester ((first Base) isostearyl acrylate), (methyl) acrylic acid nonadecane base ester, (methyl) acrylic acid eicosane base ester etc..
As above-mentioned (methyl) acrylic acid derivative containing functional group, it can be mentioned, for example：(methyl) acrylic acid 2- hydroxyl second Ester, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 3- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxybutyls, (first Base) hydroxyls such as acrylic acid 3- hydroxybutyls, (methyl) acrylic acid 4- hydroxybutyls (methyl) acrylate；(methyl) propylene Amide, N, N- dimethyl (methyl) acrylamide, N- butyl (methyl) acrylamide, N- methylols (methyl) acrylamide, N- Hydroxymethyl-propane (methyl) acrylamide, N- methoxies (methyl) acrylamide, N- butoxymethyls (methyl) acryloyl (methyl) acrylamide such as amine and its derivative；(methyl) acrylate (hereinafter also referred to " amino-containing (first with amino Base) acrylate ")；(the first of monosubstituted amino that 1 hydrogen atom with amino is replaced by the group other than hydrogen atom Base) acrylate (hereinafter also referred to " (methyl) acrylate containing monosubstituted amino ")；2 hydrogen atoms with amino are by hydrogen (methyl) acrylate of disubstituted amino that group substitution other than atom forms is (hereinafter also referred to " containing disubstituted amino (methyl) acrylate ")；(methyl) glycidyl acrylate, (methyl) acrylic acid methylglycidyl esters etc. have epoxy (methyl) acrylate (hereinafter also referred to " (methyl) acrylate containing epoxy group ") of base etc..
Here, " amino-containing (methyl) acrylate " refers to 1 or 2 of (methyl) acrylate or more hydrogen atom quilt Amino (- NH2) replace the compound formed.Similarly, " (methyl) acrylate containing monosubstituted amino " refers to (methyl) third 1 of olefin(e) acid ester or 2 or more hydrogen atom is mono-substituted the compound that amino substitution forms, " (methyl) containing disubstituted amino Acrylate " refers to the compound that 1 or 2 of (methyl) acrylate or more hydrogen atom is replaced by disubstituted amino.
(replace as the group other than the hydrogen atom of the substitution hydrogen atom in " monosubstituted amino " and " disubstituted amino " Base), it can be mentioned, for example alkyl etc..
As above-mentioned (methyl) acrylate with aliphatic ring type group, it can be mentioned, for example：(methyl) acrylic acid is different Norbornene ester, (methyl) acrylic acid dicyclopentenyl ester, (methyl) dicyclopentanyl acrylate, (methyl) acrylic acid dicyclopentenyl oxygroup second Ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid Buddha's warrior attendant alkyl ester etc..
As above-mentioned (methyl) acrylate with aromatic hydrocarbyl, it can be mentioned, for example：(methyl) phenylethyl hydroxyl Base propyl ester, (methyl) benzyl acrylate, (methyl) acrylic acid 2- hydroxyl -3- phenoxy-propyls etc..
Hetero ring type group in above-mentioned (methyl) acrylate with hetero ring type group can be heteroaromatic formula base Arbitrary group in group and aliphatic heterocycle formula group.
As (methyl) acrylate with above-mentioned hetero ring type group, it can be mentioned, for example：(methyl) acrylic acid tetrahydrochysene chaff Ester, (methyl) acryloyl morpholine etc..
As the above-mentioned compound with vinyl, it can be mentioned, for example：Styrene, hydroxyethyl vinyl ether, hydroxyl fourth Base vinyl ethers, N- vinyl formamides, n-vinyl pyrrolidone, N- caprolactams etc..
As the above-mentioned compound with pi-allyl, it can be mentioned, for example：Allyl glycidyl ether etc..
Consider from this respect good with the compatibility of above-mentioned carbamate (methyl) acrylate, above-mentioned polymerizable monomer It is preferred that with the larger group of volume.As such polymerizable monomer, it can be mentioned, for example (the first with aliphatic ring type group Base) acrylate, (methyl) acrylate with aromatic hydrocarbyl, (methyl) acrylate with hetero ring type group, more Preferably there is (methyl) acrylate of aliphatic ring type group.
The polymerizable monomer contained in 1st middle layer formation composition (II-1) can be only one kind or two Kind or more, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
In the 1st middle layer formation in composition (II-1), the content of polymerizable monomer is preferably 10~99 mass %, more Preferably 15~95 mass %, further preferably 20~90 mass %, particularly preferably 25~80 mass %.
[Photoepolymerizationinitiater initiater]
1st middle layer, which is formed, to be used in composition (II-1) in addition to above-mentioned carbamate (methyl) acrylate and polymerism Other than monomer, Photoepolymerizationinitiater initiater can also be contained.For the 1st middle layer formation composition containing Photoepolymerizationinitiater initiater (II-1), even if having irradiated the energy line compared with low energy such as ultraviolet light, curing reaction can be also sufficiently carried out.
As the 1st middle layer formation above-mentioned Photoepolymerizationinitiater initiater of composition (II-1), can enumerate and the 1st adhesive group Close identical those of Photoepolymerizationinitiater initiater in object (I-1).
The Photoepolymerizationinitiater initiater contained in 1st middle layer formation composition (II-1) can be only it is a kind of or Two or more, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
In the 1st middle layer formation in composition (II-1), relative to above-mentioned carbamate (methyl) acrylate and 100 mass parts of total content of polymerizable monomer, the content of Photoepolymerizationinitiater initiater are preferably 0.01~20 mass parts, are more preferably 0.03~10 mass parts, particularly preferably 0.05~5 mass parts.
[resin component other than carbamate (methyl) acrylate]
1st middle layer is formed can also contain above-mentioned ammonia with composition (II-1) in the range of effect of the present invention is not destroyed Resin component other than carbamate (methyl) acrylate.
The type of above-mentioned resin component and its 1st middle layer formation with the content in composition (II-1) according to purpose and Appropriate selection, is not particularly limited.
[other additives]
1st middle layer is formed in the range of effect of the present invention is not destroyed to be contained with composition (II-1) and is not belonging to Other additives of any ingredient in above-mentioned.
As above-mentioned other additives, it can be mentioned, for example：Crosslinking agent, antistatic agent, antioxidant, chain-transferring agent, softening agent Additive well known to (plasticizer), packing material, antirust agent, colorant (pigment, dyestuff) etc..
For example, as above-mentioned chain-transferring agent, can enumerate Thiolation at least one thiol base (sulfydryl) in 1 molecule Close object.
As above-mentioned mercaptan compound, it can be mentioned, for example：Nonyl mercaptan, 1- dodecyl mercaptans, 1,2- dithioglycols, 1,3- third Two mercaptan, triazine thiol, two mercaptan of triazine, three mercaptan of triazine, trithioglycerin, bis- (the 3- mercaptopropionic acids of tetraethylene glycol Ester), trimethylolpropane tris (3-thiopropionate), pentaerythrite four (3-thiopropionate), pentaerythrite tetrathio glycol Ester, dipentaerythritol six (3-thiopropionate), three [(3- mercaptopropionyls oxygroup) ethyl] isocyanuric acid esters, bis- (the 3- mercaptos of 1,4- Base butyryl acyloxy) butane, pentaerythrite four (3- mercaptobutylates), 1,3,5- tri- (3- sulfydryls butoxyethyl group) -1,3,5- three Piperazine -2,4,6- (1H, 3H, 5H)-triketone etc..
The other additives contained in 1st middle layer formation composition (II-1) can be only one kind or two Kind or more, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
In the 1st middle layer formation in composition (II-1), the content of other additives is not particularly limited, according to its kind Class suitably selects.
[solvent]
Solvent can also be contained in 1st middle layer formation composition (II-1).1st middle layer is formed with composition (II- 1) it by containing solvent, is improved relative to the coating adaptability of coating object surface.
《The manufacturing method of 1st middle layer formation composition》
The above-mentioned 1st middle layer formation composition such as the 1st middle layer formation composition (II-1) can be by that will be used for structure It is obtained into its each components matching.
Order of addition during each ingredient is coordinated to be not particularly limited, two or more ingredients can also be added simultaneously.
In the case of using solvent, this can be matched by being mixed with the arbitrary gradation composition in addition to solvent solvent Synthesis divide beforehand dilution after use, the arbitrary gradation composition other than solvent can not also be diluted in advance, but pass through by Solvent is mixed with these gradation compositions and is used.
For the method that each ingredient mixes is not particularly limited during cooperation, from rotate stirrer or agitating paddle etc. and into The method of row mixing, using method that mixer is mixed, apply in method well known to method that ultrasonic wave mixed etc. Appropriate selection.
The temperature and time when addition and mixing of each ingredient is not as long as long as causing in the case of each gradation composition deterioration It is not particularly limited, it is appropriate to adjust, but preferable temperature is 15~30 DEG C.
◎ thermoset resin layers
Above-mentioned thermoset resin layer (thermosetting resin film) is for protecting the circuit face of semiconductor wafer and being arranged on this The layer of convex block in circuit face, by being solidified to form the 1st protective film.
As described above, above-mentioned thermoset resin layer is to be heated up since state before curing with 10 DEG C/minute of heating rate When, Δ t1 is the resin layer of 500 seconds or more.
In addition, above-mentioned thermoset resin layer the thermoset resin layer formation composition containing its constituent material can be used and It is formed.
Therefore, the Δ t1 of above-mentioned thermoset resin layer can by adjust thermoset resin layer formation composition contain into Point type and amount in any one or both and adjusted.
About thermoset resin layer formation composition and its manufacturing method, then it is described in detail.
For example, by reduce thermoset resin layer formation composition containing particularly make viscosity increased in ingredient into Divide the content in above-mentioned composition, can more easily adjust Δ t1 to preferred range.Increase viscosity as above-mentioned Ingredient, it can be mentioned, for example aftermentioned packing material (D) etc., but it's not limited to that.
In addition, for example, particularly subtract viscosity by increasing containing in ingredient for thermoset resin layer formation composition Content of the small ingredient in above-mentioned composition can more easily be adjusted Δ t1 to preferred range.Make to glue as above-mentioned The ingredient reduced is spent, it can be mentioned, for example aftermentioned thermoplastic resin etc., but it's not limited to that.
In addition, for example, by reduce thermoset resin layer formation composition containing in ingredient particularly thermosetting property into The more stable ingredient of content or using effect point in above-mentioned composition, can be more easily by Δ as thermosetting component T1 is adjusted to preferred range.Above-mentioned thermosetting component for example can be from aftermentioned thermosetting component (B) (for example, epoxy resin (B1) and thermal curing agents (B2)) etc. in suitably select, but it's not limited to that.
As preferred thermoset resin layer, it can be mentioned, for example consolidating containing component of polymer (A) and thermosetting component (B) The property changed resin film.Component of polymer (A) is regarded as the ingredient formed by the aggregated reaction of polymerizable compound.It is in addition, hot Solidity ingredient (B) is the ingredient that the triggering factor that can be with heat to react is cured (polymerization) reaction.It should be noted that In the present invention, polymerisation also includes polycondensation reaction.
Above-mentioned thermoset resin layer can be only one layer (individual layer) or more than two layers of multilayer, be the feelings of multilayer Under condition, which mutually can be the same or different, and the combination of the multilayer is not particularly limited.
In the case that above-mentioned thermoset resin layer is multilayer, thermoset resin layer integrally meets the condition of above-mentioned Δ t1 i.e. It can.
The thickness of above-mentioned thermoset resin layer is preferably 1~100 μm, more preferably 5~75 μm, particularly preferably 5~50 μ m.By making the thickness of thermoset resin layer more than above-mentioned lower limiting value, higher 1st protective film of protective capability can be formed.Separately Outside, by making the thickness of thermoset resin layer in above-mentioned upper limit value hereinafter, inhibiting the 1st protective film further containing bladdery effect It improves.
Here, " thickness of thermoset resin layer " represents the thickness of thermoset resin layer entirety, for example, be made up of multiple layers The thickness of thermoset resin layer refers to form the aggregate thickness of whole layers of thermoset resin layer.
《Thermoset resin layer formation composition》
The thermoset resin layer formation containing its constituent material can be used to be formed with composition for thermoset resin layer.For example, By applying thermoset resin layer formation composition in the formation object surface of thermoset resin layer and making it dry as needed It is dry, thermoset resin layer can be formed at the position of target.Do not occur under room temperature in thermoset resin layer formation composition The content ratio of the ingredient of gasification to each other is usually identical with the content ratio of the mentioned component of thermoset resin layer to each other.This In, " room temperature " as previously described.
The coating that thermoset resin layer forms composition is carried out using well known method, and it can be mentioned, for example use gas Knife coating machine, bar coater, gravure coater, roll coater, roller knife coating machine, curtain stream coating machine, die coating machine, is scraped scraper plate coating machine The method of the various coating machines such as knife coating machine, silk screen coating machine, Meyer bar coater, kiss coater.
The drying condition of thermoset resin layer formation composition is not particularly limited, but is formed and used in thermoset resin layer In the case that composition contains aftermentioned solvent, preferably it is thermally dried.Thermoset resin layer containing solvent is formed It is preferably dried with composition with the condition for example carried out in 70~130 DEG C 10 seconds~5 minutes.
<Resin layer is formed with composition (III-1)>
As thermoset resin layer formation composition, it can be mentioned, for example：Contain component of polymer (A) and thermosetting component (B) thermoset resin layer is formed with composition (III-1) (in the present specification, also referred to as " resin layer formation composition (III-1) ") etc..
[component of polymer (A)]
Component of polymer (A) is used to the polymer compound that thermoset resin layer assigns film forming, flexibility etc..
The component of polymer (A) contained in resin layer formation composition (III-1) and thermoset resin layer can be only A kind of or two or more, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
As component of polymer (A), it can be mentioned, for example：Acrylic resin (resin with (methyl) acryloyl group), Polyester, urethane based resin (resin with amino-formate bond), propenoic methyl carbamate resin, organic silicon tree Fat (resin with siloxanes key), rubber resin (resin with rubber structure), phenoxy resin, Thermocurable polyimide Deng preferably acrylic resin.
As the above-mentioned acrylic resin in component of polymer (A), well known acrylate copolymer can be enumerated.
The weight average molecular weight (Mw) of acrylic resin is preferably 10000~2000000, more preferably 100000~ 1500000.It is more than above-mentioned lower limiting value by the weight average molecular weight for making acrylic resin, the shape of thermoset resin layer is steady Qualitative (ageing stability during keeping) improves.In addition, by the way that the weight average molecular weight of acrylic resin is made to be above-mentioned upper limit value Hereinafter, thermoset resin layer easily follows the male and fomale(M＆F) of adherend.
The glass transition temperature (Tg) of acrylic resin is preferably -60~70 DEG C, more preferably -30~50 DEG C.It is logical Crossing makes the Tg of acrylic resin the bonding force between the 1st protective film and the 1st support chip is pressed down more than above-mentioned lower limiting value System, the fissility of the 1st support chip improve.In addition, by making the Tg of acrylic resin in above-mentioned upper limit value hereinafter, and thermosetting property Bonding force between the adherend of resin layer and the 1st protective film improves.
As acrylic resin, it can be mentioned, for example：The polymer of one or more kinds of (methyl) acrylate；It is selected from It is two or more in (methyl) acrylic acid, itaconic acid, vinyl acetate, acrylonitrile, styrene and N hydroxymethyl acrylamide etc. Copolymer of monomer etc..
As form acrylic resin above-mentioned (methyl) acrylate, it can be mentioned, for example：(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (first Base) isobutyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) 2-EHA, (methyl) Isooctyl acrylate monomer, (methyl) N-octyl, the positive nonyl ester of (methyl) acrylic acid, the different nonyl ester of (methyl) acrylic acid, (methyl) decyl acrylate, (methyl) third Olefin(e) acid hendecane base ester, (methyl) dodecylacrylate ((methyl) lauryl acrylate), (methyl) acrylic acid tridecane Base ester, (methyl) acrylic acid tetradecane base ester ((methyl) myristyl ester), (methyl) acrylic acid pentadecane base ester, (first Base) aliphatic acrylate ((methyl) acrylic acid palm ester), (methyl) acrylic acid heptadecane base ester, (methyl) acrylic acid ten The alkyl that eight Arrcostabs ((methyl) stearyl acrylate) etc. form Arrcostab is the chain structure that carbon atom number is 1~18 (methyl) alkyl acrylate；
(methyl) the acrylate base esters such as (methyl) isobornyl acrylate, (methyl) dicyclopentanyl acrylate；
(methyl) benzyl acrylate etc. (methyl) acrylic acid aralkyl ester；
(methyl) acrylic acid cyclenes base ester such as (methyl) acrylic acid dicyclopentenyl ester；
(methyl) acrylic acid cyclenes oxygroup Arrcostab such as (methyl) acrylic acid dicyclopentenyl oxygroup ethyl ester；
(methyl) propylene acid imide；
(methyl) acrylate containing glycidyl such as (methyl) glycidyl acrylate；
(methyl) dihydroxypropyl methyl esters, (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 3- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxybutyls, (methyl) acrylic acid 3- hydroxybutyls, (methyl) third (methyl) acrylate of the hydroxyls such as olefin(e) acid 4- hydroxybutyls；
(methyl) acrylate containing substituted-amino such as (methyl) acrylic acid N- methylamino ethyl esters etc..Here, " substitution ammonia The group that base " refers to 1 of amino or 2 hydrogen atoms are replaced by the group other than hydrogen atom.
Acrylic resin for example can also be selected from (methyl) third by above-mentioned (methyl) acrylate and in addition to it One or more of olefin(e) acid, itaconic acid, vinyl acetate, acrylonitrile, styrene and N hydroxymethyl acrylamide etc. are single Body copolymerization forms.
It can be only a kind of or two or more to form the monomer of acrylic resin, be two or more situations Under, combination thereof and ratio can be selected arbitrarily.
Acrylic resin can also have vinyl, (methyl) acryloyl group, amino, hydroxyl, carboxyl, isocyanate group Etc. the functional group that can be bonded with other compounds.The above-mentioned functional group of acrylic resin can be via crosslinking described later Agent (F) and be bonded with other compounds, can not also be bonded via crosslinking agent (F) with other compounds.By making acrylic acid Resinoid is bonded using above-mentioned functional group with other compounds, using packaging body obtained from the 1st protective film formation piece can There is the tendency improved by property.
In the present invention, as component of polymer (A), acrylic resin can not used and acrylic compounds is used alone Thermoplastic resin (hereinafter also referred to as " thermoplastic resin ") other than resin, can also be by the thermoplastic other than acrylic resin Property resin is applied in combination with acrylic resin.By using above-mentioned thermoplastic resin, can improve sometimes the 1st protective film relative to The fissility of 1st support chip causes thermoset resin layer easily to follow the male and fomale(M＆F) of adherend.
The weight average molecular weight of above-mentioned thermoplastic resin is preferably 1000~100000, more preferably 3000~80000.
The glass transition temperature (Tg) of above-mentioned thermoplastic resin is preferably -30~150 DEG C, is more preferably -20~120 ℃。
As above-mentioned thermoplastic resin, it can be mentioned, for example：Polyester, phenoxy resin, polybutene, polybutadiene, gathers polyurethane Styrene etc..
The above-mentioned thermoplastic resin contained in resin layer formation composition (III-1) and thermoset resin layer can be only A kind of or two or more, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
In resin layer formation in composition (III-1), the content of component of polymer (A) is relative to the whole other than solvent The ratio (that is, content of the component of polymer (A) in thermoset resin layer) of the total content of ingredient is independent of component of polymer (A) type, preferably 5~85 mass %, more preferably 5~80 mass % or such as 5~70 mass %, 5~60 Arbitrary proportion in quality %, 5~50 mass %, 5~40 mass % and 5~30 mass %.It should be noted that resin layer Formed with these contents in composition (III-1) only as an example of.
Component of polymer (A) also corresponds to thermosetting component (B) sometimes.In the present invention, it is combined in resin layer formation In the case that object (III-1) is containing such ingredient for being equivalent to both component of polymer (A) and thermosetting component (B), depending on To contain component of polymer (A) and thermosetting component (B) in resin layer formation composition (III-1).
[thermosetting component (B)]
Thermosetting component (B) be for make thermoset resin layer be solidified to form hard the 1st protective film ingredient.
The thermosetting component (B) contained in resin layer formation composition (III-1) and thermoset resin layer can be only A kind of or two or more, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
As thermosetting component (B), it can be mentioned, for example：Epoxy-based thermosetting resin, Thermocurable polyimide, polyurethane, Unsaturated polyester (UP), organic siliconresin etc., preferably epoxy-based thermosetting resin.
(epoxy-based thermosetting resin)
Epoxy-based thermosetting resin includes epoxy resin (B1) and thermal curing agents (B2).
The epoxy-based thermosetting resin contained in resin layer formation composition (III-1) and thermoset resin layer can be only To be a kind of or two or more, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
Epoxy resin (B1)
As epoxy resin (B1), well known epoxy resin can be enumerated, it can be mentioned, for example：Multifunctional based epoxy resin, connection Benzene compound, bisphenol A diglycidyl ether and its hydrogenation products, o-cresol phenolic resin varnish, dicyclopentadiene type ring Oxygen resin, biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenylene matrix type epoxy resin etc., And epoxide more than difunctionality.
As epoxy resin (B1), the epoxy resin with unsaturated alkyl can also be used.With without unsaturated hydrocarbons The epoxy resin of base is compared, and has the epoxy resin of unsaturated alkyl and the compatibility higher of acrylic resin.Therefore, pass through Using the epoxy resin with unsaturated alkyl, improved using the reliability of packaging body obtained from the 1st protective film formation piece.
As the epoxy resin with unsaturated alkyl, it can be mentioned, for example：The one of the epoxy group of multifunctional based epoxy resin It is partly converted into the compound that the group with unsaturated alkyl forms.Such compound for example can be by making (methyl) third Olefin(e) acid or derivatives thereof carries out addition reaction with epoxy group and obtains.
In addition, as the epoxy resin with unsaturated alkyl, it can be mentioned, for example：Group with unsaturated alkyl is direct It is bonded to compounds formed such as the aromatic ring for forming epoxy resin etc..
Unsaturated alkyl is the unsaturated group for having polymerism, as its concrete example, can enumerate vinyl (vinyl Group, ethenyl group), 2- acrylic (pi-allyl), (methyl) acryloyl group, (methyl) acrylamido etc., preferably For acryloyl group.
The number-average molecular weight of epoxy resin (B1) is not particularly limited, but curability from thermoset resin layer, Yi Jigu From the aspect of the 1st protection film strength and heat resistance after change, preferably 300~30000, more preferably 400~10000, it is special It You Xuanwei 500~3000.
The epoxide equivalent of epoxy resin (B1) is preferably 100~1000g/eq, more preferably 300~800g/eq.
Epoxy resin (B1) can be used alone, and can also be used in combination of two or more, be applied in combination two kinds with In the case of upper, combination thereof and ratio can be selected arbitrarily.
Thermal curing agents (B2)
Thermal curing agents (B2) are functioned as the curing agent of epoxy resin (B1).
As thermal curing agents (B2), it can be mentioned, for example：It can be with the official of epoxy reaction with 2 or more in 1 molecule The compound that can be rolled into a ball.As above-mentioned functional group, it can be mentioned, for example：Phenolic hydroxyl group, alcoholic extract hydroxyl group, amino, carboxyl, acidic group through acid anhydrides and Into group etc., the group that preferably phenolic hydroxyl group, amino or acidic group are formed through acid anhydrides, more preferably phenolic hydroxyl group or amino.
As the phenols curing agent with phenolic hydroxyl group in thermal curing agents (B2), it can be mentioned, for example：Multifunctional phenolic resin, Xenol, novolak phenolics, dicyclopentadiene class phenolic resin, aralkyl phenolic resin etc..
As the amine curing agent with amino in thermal curing agents (B2), it can be mentioned, for example：Dicyandiamide is (below also referred to as For " DICY ") etc..
Thermal curing agents (B2) can also be the thermal curing agents for having unsaturated alkyl.
As the thermal curing agents (B2) with unsaturated alkyl, it can be mentioned, for example：A part of quilt of the hydroxyl of phenolic resin Group with unsaturated alkyl replaces the compound formed, the group with unsaturated alkyl to be bonded directly to phenolic resin Compound that aromatic ring forms etc..
Above-mentioned unsaturated alkyl in thermal curing agents (B2) be in the above-mentioned epoxy resin with unsaturated alkyl not The identical group of saturated hydrocarbyl.
In the case of using phenols curing agent as thermal curing agents (B2), from the 1st protective film is improved relative to the 1st support chip Fissility from the perspective of, thermal curing agents (B2) are preferably softening point or the high thermal curing agents of glass transition temperature.
For example multifunctional phenolic resin, novolak phenolics, dicyclopentadiene class phenol in thermal curing agents (B2) The number-average molecular weight of the resin components such as urea formaldehyde, aralkyl phenolic resin is preferably 300~30000, more preferably 400~ 10000th, 500~3000 are particularly preferably.
The molecular weight of non-resin ingredient such as xenol, dicyandiamide in thermal curing agents (B2) is not particularly limited, but Preferably such as 60~500.
Thermal curing agents (B2) can be used alone, and can also be used in combination of two or more, be applied in combination two kinds with In the case of upper, combination thereof and ratio can be selected arbitrarily.
In resin layer formation in composition (III-1) and thermoset resin layer, relative to the content of epoxy resin (B1) 100 mass parts, the content of thermal curing agents (B2) is preferably 0.1~500 mass parts, more preferably 1~200 mass parts, for example, can To be the arbitrary content in 5~100 mass parts, 10~80 mass parts and 15~60 mass parts.By making thermal curing agents (B2) More than above-mentioned lower limiting value, the curing of thermoset resin layer can become easier to carry out above-mentioned content.In addition, by making heat cure The above-mentioned content of agent (B2) is in above-mentioned upper limit value hereinafter, the hydroscopicity of thermoset resin layer is reduced, formed and used using the 1st protective film The reliability of packaging body obtained from piece further improves.
In resin layer formation in composition (III-1) and thermoset resin layer, relative to the content of component of polymer (A) 100 mass parts, the content (for example, total content of epoxy resin (B1) and thermal curing agents (B2)) of thermosetting component (B) is preferably 50~1000 mass parts, more preferably 100~900 mass parts, particularly preferably 150~800 mass parts or such as Arbitrary content in 200~700 mass parts and 250~650 mass parts.By making the above-mentioned content of thermosetting component (B) at this In the range of sample, the bonding force between the 1st protective film and the 1st support chip is inhibited, and the fissility of the 1st support chip improves.
[curing accelerator (C)]
Resin layer formation composition (III-1) and thermoset resin layer can also contain curing accelerator (C).Curing promotees It is for adjusting the ingredient of the curing rate of resin layer formation composition (III-1) into agent (C).
As preferred curing accelerator (C), it can be mentioned, for example：Triethylenediamine, benzyldimethylamine, 2,4, three ethyl alcohol The tertiary amines such as amine, dimethylaminoethanol, three (dimethylaminomethyl) phenol；2-methylimidazole, 2- phenylimidazoles, 2- phenyl- The imidazoles (1 such as 4-methylimidazole, 2- phenyl -4,5- bishydroxymethyls imidazoles, 2- phenyl -4- methyl -5- hydroxymethylimidazoles The imidazoles that more than hydrogen atom is replaced by the group other than hydrogen atom)；Tributylphosphine, diphenylphosphine, triphenylphosphine etc. are organic Phosphine (phosphine that 1 or more hydrogen atom is replaced by organic group)；Tetraphenylphosphoniphenolate tetraphenyl borate salts, triphenylphosphine tetraphenyl Tetraphenyl borate salts such as borate etc..
The curing accelerator (C) contained in resin layer formation composition (III-1) and thermoset resin layer can be only A kind of or two or more, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
In the case of using curing accelerator (C), in resin layer formation composition (III-1) and thermoset resin layer In, relative to 100 mass parts of content of thermosetting component (B), the content of curing accelerator (C) is preferably 0.01~10 mass Part, more preferably 0.05~5 mass parts, for example, it can be 0.1~5 mass parts.By making the above-mentioned of curing accelerator (C) Content can be obtained significantly more more than above-mentioned lower limiting value using effect caused by curing accelerator (C).In addition, by making The content of curing accelerator (C) is in above-mentioned upper limit value hereinafter, for example for highly polar highly polar curing accelerator (C) in height Mobile to the bonding interface side with adherend in the thermoset resin layer and inhibition that is segregated under temperature/super-humid conditions It further improves, is further improved using the 1st protective film formation reliability of packaging body obtained from piece.
[packing material (D)]
Resin layer formation composition (III-1) and thermoset resin layer can also contain packing material (D).By making heat Thermosetting resin layer contains packing material (D), for making the coefficient of thermal expansion of the 1st protective film obtained from thermoset resin layer cures Adjustment become easy.And then the coefficient of thermal expansion is optimized by the formation object relative to the 1st protective film, use the 1st Protective film formation reliability of packaging body obtained from piece further improves.In addition, it is filled out by containing thermoset resin layer Material (D) is filled, the hydroscopicity of the 1st protective film can also be reduced, improve exothermicity.
Packing material (D) can be any materials in organic filler material and inorganic filling material, but preferably inorganic Packing material.
As preferred inorganic filling material, it can be mentioned, for example：Silica, aluminium oxide, talcum, calcium carbonate, titanium white, iron The powder such as red, silicon carbide, boron nitride；The spherical bead formed is made in these inorganic filling materials；These inorganic filling materials Surface be modified product；The mono-crystlling fibre of these inorganic filling materials；Glass fibre etc..
In these materials, preferably inorganic filling material is silica or aluminium oxide.
The packing material (D) contained in resin layer formation composition (III-1) and thermoset resin layer can be only one It plants or two or more, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
In the case of using packing material (D), in resin layer formation in composition (III-1), packing material (D's) contains Measure the ratio (that is, content of the packing material (D) of thermoset resin layer) of the total content relative to whole ingredients other than solvent Preferably 5~35 mass %, more preferably 5~30 mass % or such as 7~25 mass %.By making packing material (D) content is more than above-mentioned lower limiting value, and the adjusting of above-mentioned coefficient of thermal expansion becomes more easy, by making packing material (D) content is in above-mentioned upper limit value hereinafter, the adjusting of Δ t1 becomes more easy.
In the present invention, from the viewpoint of making the adjusting of Δ t1 more easy, in resin layer formation composition (III- 1) in, the content of packing material (D) is relative to the ratio of the total content of whole ingredients other than solvent (that is, thermoset resin layer Packing material (D) content) be preferably below 35 mass %, more preferably below 30 mass % or such as 25 matter % is measured hereinafter, can also be 0 mass %.
[coupling agent (E)]
Resin layer formation composition (III-1) and thermoset resin layer can also contain coupling agent (E).By using tool Thermosetting property tree can be made with the compound of inorganic compound or the functional group of organic compound reaction as coupling agent (E) by having Lipid layer is improved relative to the cementability and adaptation of adherend.In addition, by using coupling agent (E), will not cause to make thermosetting Property resin layer curing obtain the heat resistance of the 1st protective film and be damaged, water resistance can be improved.
Coupling agent (E) preferably has can be with functional group possessed by component of polymer (A), thermosetting component (B) etc. The compound of the functional group of reaction, more preferably silane coupling agent.
As preferred above-mentioned silane coupling agent, it can be mentioned, for example：3- glycidoxypropyltrime,hoxysilanes, 3- rings Oxygen propoxypropyl methyldiethoxysilane, 3- glycidoxypropyl groups triethoxysilane, 3- glycidyl oxy methyls two Ethoxysilane, 2- (3,4- epoxycyclohexyls) ethyl trimethoxy silane, 3- methacryloxypropyl trimethoxy silicon Alkane, 3- TSL 8330s, 3- (2- aminoethylaminos) propyl trimethoxy silicane, 3- (2- amino-ethyl ammonia Base) hydroxypropyl methyl diethoxy silane, 3- (phenyl amino) propyl trimethoxy silicane, 3- anilino- propyl trimethoxy silicon It is alkane, 3- ureas propyl-triethoxysilicane, 3-mercaptopropyi trimethoxy silane, 3- mercaptopropyis methyl dimethoxysilane, double (3- triethoxysilylpropyltetrasulfides) tetrasulfide, methyltrimethoxysilane, methyltriethoxysilane, vinyl front three Oxysilane, vinyltriacetoxy silane and imidizole silane etc..
The coupling agent (E) contained in resin layer formation composition (III-1) and thermoset resin layer can be only one kind, Can also be two or more, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
In the case of using coupling agent (E), in resin layer formation in composition (III-1) and thermoset resin layer, phase For 100 mass parts of total content of component of polymer (A) and thermosetting component (B), the content of coupling agent (E) is preferably 0.03~ 20 mass parts, more preferably 0.05~10 mass parts, particularly preferably 0.1~5 mass parts.By making the above-mentioned of coupling agent (E) Content can significantly more obtain raising, the thermosetting property tree of dispersibility of the packing material (D) in resin more than above-mentioned lower limiting value Raising of the cementability of lipid layer and adherend etc. uses effect caused by coupling agent (E).In addition, by making coupling agent (E) Above-mentioned content in above-mentioned upper limit value hereinafter, the generation of degassing (outgas) can be further suppressed.
[crosslinking agent (F)]
There is vinyl, (methyl) propylene that can be bonded with other compounds using above-mentioned acrylic resin etc. In the case that the ingredient of the functional groups such as acyl group, amino, hydroxyl, carboxyl, isocyanate group is as component of polymer (A), resin layer Formation composition (III-1) and thermoset resin layer can also contain crosslinking agent (F).Crosslinking agent (F) is for making polymer The ingredient that above-mentioned functional group in ingredient (A) is bonded with other compounds and is crosslinked, is crosslinked in this way, can It is adjusted with the initial bond power and cohesiveness to thermoset resin layer.
As crosslinking agent (F), it can be mentioned, for example：Organic polyisocyanate compound, organic more group with imine moiety, metal chelating Close species crosslinking agent (crosslinking agent with metallo-chelate structure), aziridines crosslinking agent (crosslinking agent with '-aziridino) Deng.
As above-mentioned organic polyisocyanate compound, it can be mentioned, for example：Aromatic polyisocyanate compound, aliphatic These compounds (are also together simply referred to as " aromatic series by polyisocyanate compound and alicyclic polyisocyanates compound below Polyisocyanate compound etc. ")；The trimers such as above-mentioned aromatic polyisocyanate compound, isocyanuric acid ester body and adduct； Terminal isocyanate carbamic acid obtained from making above-mentioned aromatic polyisocyanate compound etc. and polyol compound reaction Ester prepolymer etc..Above-mentioned " adduct " represents above-mentioned aromatic polyisocyanate compound, aliphatic polyisocyanate compound Or the low molecules such as alicyclic polyisocyanates compound and ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane or castor oil The reactant of active hydrogen compounds.As the example of above-mentioned adduct, trimethylolpropane as described later can be enumerated Benzene dimethylene diisocyanate addition product etc..In addition, " the terminal isocyanate carbamate prepolymer " such as institute above It states.
As above-mentioned organic polyisocyanate compound, more specifically, it can be mentioned, for example：2,4 toluene diisocyanate； 2,6- toluene di-isocyanate(TDI)s；1,3- benzene dimethylene diisocyanate；1,4- xylene diisocyanate；Diphenyl methane- 4,4 '-diisocyanate；Diphenyl methane -2,4 '-diisocyanate；3- Dimethyl diphenylmethane diisocyanate；Six methylenes Group diisocyanate；Isophorone diisocyanate；Dicyclohexyl methyl hydride -4,4 '-diisocyanate；Dicyclohexyl methyl hydride -2, 4 '-diisocyanate；Addition has toluene di-isocyanate(TDI), six Asias on all or part of hydroxyl of the polyalcohols such as trimethylolpropane Any one in methyl diisocyanate and benzene dimethylene diisocyanate or the two or more compounds formed；Lysine Diisocyanate etc..
As above-mentioned organic more group with imine moiety, it can be mentioned, for example：N, N '-diphenyl methane -4,4 '-bis- (1- aziridine Formamide) ,-three-β of trimethylolpropane-'-aziridino propionic ester ,-three-β of tetramethylol methane-'-aziridino propionic ester, N, Bis- (1- aziridine formamide) triethylenemelanins of N '-Toluene-2,4-diisocyanate, 4- etc..
It is excellent as component of polymer (A) in the case where using organic polyisocyanate compound as crosslinking agent (F) Choosing uses the polymer of hydroxyl.Crosslinking agent (F) with isocyanate group, component of polymer (A) with hydroxyl in the case of, Can by crosslinking agent (F) and component of polymer (A) react easily import cross-linked structure to thermoset resin layer.
The crosslinking agent (F) contained in resin layer formation composition (III-1) and thermoset resin layer can be only one kind, Can also be two or more, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
In the case of using crosslinking agent (F), in resin layer formation in composition (III-1), relative to component of polymer (A) 100 mass parts of content, the content of crosslinking agent (F) be preferably 0.01~20 mass parts, more preferably 0.1~10 mass parts, Particularly preferably 0.5~5 mass parts.By making the above-mentioned content of crosslinking agent (F) that can significantly more be obtained more than above-mentioned lower limiting value Obtain the effect for using crosslinking agent (F) and bringing.In addition, by making the above-mentioned content of crosslinking agent (F) in above-mentioned upper limit value hereinafter, can Inhibit being excessively used for crosslinking agent (F).
[energy ray-curable resin (G)]
Resin layer formation composition (III-1) can also contain energy ray-curable resin (G).Thermoset resin layer leads to It crosses containing energy ray-curable resin (G), can characteristic be changed based on the irradiation of energy line.
Energy ray-curable resin (G) is to make resin obtained from energy ray-curable compound polymerization (curing).
As above-mentioned energy ray-curable compound, it can be mentioned, for example：Intramolecular at least has the change of 1 polymeric double bond Close object, it is however preferred to have the acrylic ester compound of (methyl) acryloyl group.
As above-mentioned acrylic ester compound, it can be mentioned, for example：Trimethylolpropane tris (methyl) acrylate, four hydroxyls Methylmethane four (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, two Pentaerythrite monohydroxy five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, 1,4- butanediols two (methyl) (methyl) acrylate of the skeletons of race containing chain fatty such as acrylate, 1,6-HD two (methyl) acrylate；Two (first Base) skeleton containing annular aliphatic such as dicyclopentanyl acrylate (methyl) acrylate；Polyethylene glycol two (methyl) acrylate Etc. polyalkylene glycol (methyl) acrylate；Oligoester (methyl) acrylate；Carbamate (methyl) acrylate is low Polymers；Epoxy-modified (methyl) acrylate；Polyethers (methyl) third other than above-mentioned polyalkylene glycol (methyl) acrylate Olefin(e) acid ester；Itaconic acid oligomer etc..
The weight average molecular weight of above-mentioned energy ray-curable compound is preferably 100~30000, more preferably 300~ 10000。
It can be only a kind of or two or more for the above-mentioned energy ray-curable compound of polymerization, be two kinds In the case of above, combination thereof and ratio can be selected arbitrarily.
The energy ray-curable resin (G) contained in resin layer formation composition (III-1) can be only one kind, also may be used To be two or more, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
In the case of using energy ray-curable resin (G), resin layer forms the energy line curing with composition (III-1) Property resin (G) content be preferably 1~95 mass %, more preferably 5~90 mass %, particularly preferably 10~85 mass %.
[Photoepolymerizationinitiater initiater (H)]
In the case that resin layer formation uses composition (III-1) containing energy ray-curable resin (G), in order to make energy line The polymerisation of curable resin (G) is effectively performed, and can also contain Photoepolymerizationinitiater initiater (H).
As Photoepolymerizationinitiater initiater (H) of the resin layer formation in composition (III-1), can enumerate and the 1st adhesive group Close identical those of Photoepolymerizationinitiater initiater in object (I-1).
The Photoepolymerizationinitiater initiater (H) contained in resin layer formation composition (III-1) can be only it is a kind of or Two or more, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
In the case of using Photoepolymerizationinitiater initiater (H), in resin layer formation in composition (III-1), relative to energy 100 mass parts of content of line curable resin (G), the content of Photoepolymerizationinitiater initiater (H) is preferably 0.1~20 mass parts, more excellent It is selected as 1~10 mass parts, particularly preferably 2~5 mass parts.
[universal additive (I)]
Resin layer formation can also be in the range for not destroying effect of the present invention with composition (III-1) and thermoset resin layer It is interior to contain universal additive (I).
Universal additive (I) can be well known additive, can select, be not particularly limited according to purpose and arbitrarily, make For preferred additive, it can be mentioned, for example：Plasticizer, antistatic agent, antioxidant, colorant (dyestuff, pigment) and getter Deng.
The universal additive (I) contained in resin layer formation composition (III-1) and thermoset resin layer can be only A kind of or two or more, in the case of being two or more, combination thereof and ratio can be selected arbitrarily.
The content that resin layer forms the universal additive (I) with composition (III-1) and thermoset resin layer is not special It limits, is suitably selected according to purpose.
[solvent]
Resin layer formation composition (III-1) preferably further contains solvent.Resin layer formation group containing solvent Closing the operability of object (III-1) becomes good.
Above-mentioned solvent is not particularly limited, as preferred solvent, it can be mentioned, for example：The hydrocarbon such as toluene, dimethylbenzene；Methanol, The alcohol such as ethyl alcohol, 2- propyl alcohol, isobutanol (2- methylpropane -1- alcohol), n-butyl alcohol；The esters such as ethyl acetate；The ketone such as acetone, methyl ethyl ketone； The ethers such as tetrahydrofuran；Amides such as dimethylformamide, N-Methyl pyrrolidone (compound with amido bond) etc..
The solvent contained in resin layer formation composition (III-1) can be only a kind of or two or more, be In the case of two or more, combination thereof and ratio can be selected arbitrarily.
Gone out from resin layer formation can be made with the viewpoint mixed with being more uniformly distributed containing ingredient in composition (III-1) Hair, it is preferably methyl ethyl ketone etc. that resin layer, which is formed with the solvent contained in composition (III-1),.
<<The manufacturing method of thermoset resin layer formation composition>>
The thermoset resin layers formation such as resin layer formation composition (III-1) composition can be by that will be used to form it Each components matching and obtain.
Order of addition during each ingredient is coordinated to be not particularly limited, two or more ingredients can also be added simultaneously.
In the case of using solvent, this can be matched by being mixed with the arbitrary gradation composition in addition to solvent solvent Synthesis divide beforehand dilution after use, the arbitrary gradation composition other than solvent can not also be diluted in advance, but pass through by Solvent is mixed with these gradation compositions and is used.
For the method that each ingredient mixes is not particularly limited during cooperation, from rotate stirrer or agitating paddle etc. and into The method of row mixing, using method that mixer is mixed, apply in method well known to method that ultrasonic wave mixed etc. Appropriate selection.
The temperature and time when addition and mixing of each ingredient is not as long as long as causing in the case of each gradation composition deterioration It is not particularly limited, it is appropriate to adjust, but preferable temperature is 15~30 DEG C.
The manufacturing method of the 1st protective film formation pieces of ◇
Above-mentioned 1st protective film formation piece can by above-mentioned each layer in a manner of becoming corresponding position relationship successively It is laminated and manufactures.The forming method of each layer is as indicated above.
For example, in the case of the 1st adhesive phase or the 1st middle layer is laminated on the 1st base material when manufacturing 1 support chip, Can by applied on the 1st base material the 1st above-mentioned adhesive composition or the 1st middle layer formation composition and as needed into The 1st adhesive phase or the 1st middle layer is laminated in row drying or irradiation energy line.
On the other hand, such as it is thermosetting resin is further laminated on the 1st adhesive phase being layered on the 1st base material In the case of layer, thermoset resin layer formation can be applied on the 1st adhesive phase and directly form thermosetting property tree with composition Lipid layer.Similarly, it is in the case of the 1st adhesive phase is further laminated in the 1st middle layer being laminated on the 1st base material, The 1st adhesive composition can be applied in the 1st middle layer and directly form the 1st adhesive phase.In this way, using arbitrary group Object is closed come in the case of forming continuous two layers of stepped construction, can on the layer formed by above-mentioned composition further coating group Close object and new forming layer.Wherein, it is preferable to use above-mentioned composition is pre-formed the rear stacking in this two layers on another stripping film Layer, and by the exposed surface of the opposite side that side is contacted with above-mentioned stripping film of the established layer and established remainder layer Exposed surface is bonded, so as to form continuous two layers of stepped construction.At this point, it is preferred that above-mentioned composition is coated in the stripping of stripping film Process face.Stripping film removes as needed after stepped construction is formed.
The 1st adhesive phase is laminated on the 1st base material, thermosetting property tree is laminated on above-mentioned 1st adhesive phase for example, to manufacture The 1st protective film formation piece (1st protection of the 1st support chip for the 1st base material and the sandwich of the 1st adhesive phase that lipid layer forms Film formation piece) in the case of, by applying the 1st adhesive composition on the 1st base material and being dried as needed, from And the 1st adhesive phase is laminated on the 1st base material in advance, by additionally applying thermoset resin layer formation group on stripping film It closes object and is dried as needed, thermoset resin layer is formed on stripping film in advance, by the dew of the thermoset resin layer The exposed surface of the 1st adhesive phase with being layered on the 1st base material of appearing is bonded, and thermoset resin layer is layered in the 1st bonding In oxidant layer, this makes it possible to obtain the 1st protective film formation pieces.
The 1st middle layer is laminated on the 1st base material, the 1st bonding is laminated in above-mentioned 1st middle layer in addition, for example to manufacture In the case of the 1st support chip that oxidant layer forms, by applying the 1st middle layer formation composition on the 1st base material and according to need Will and be dried or irradiation energy line, the 1st middle layer is laminated on the 1st base material in advance, by additionally being applied on stripping film It applies the 1st adhesive composition and is dried as needed, form the 1st adhesive phase on stripping film in advance, the 1st is glued The exposed surface of 1st middle layer of the exposed surface of mixture layer with being layered on the 1st base material is bonded, and the 1st adhesive phase is layered in In 1st middle layer, this makes it possible to obtain the 1st support chips.At this point, for example further by additionally applying thermosetting property on stripping film Resin layer formation composition is simultaneously dried as needed, thermoset resin layer is formed on stripping film in advance, by the heat The exposed surface of 1st adhesive phase of the exposed surface of thermosetting resin layer with being layered in the 1st middle layer is bonded, by thermosetting resin Layer stackup is on the 1st adhesive phase, and this makes it possible to obtain the 1st protective film formation pieces.
It should be noted that in the case of the 1st adhesive phase or the 1st middle layer being laminated on the 1st base material, as above institute It states, the method that can also replace applying the 1st adhesive composition or the 1st middle layer formation composition on the 1st base material passes through The 1st adhesive composition or the 1st middle layer formation composition are applied on stripping film and is dried or shines as needed Energy line is penetrated, forms the 1st adhesive phase or the 1st middle layer on stripping film in advance and by the exposed surface of these layers and the 1st base material Side surface fitting, so that the 1st adhesive phase or the 1st middle layer are superimposed on the 1st base material.
In any method, random time point that can be after the stepped construction of target is formd removes stripping film It goes.
In this way, the layer other than the 1st base material of the 1st protective film formation piece of composition can utilize and be previously formed in stripping film It goes up and fits in the method on the surface of the layer of target and be laminated, therefore, as long as suitably selecting using so as needed The layer of process manufacture the 1st protective film formation piece.
It should be noted that the 1st protective film formation with piece usually on the most surface layer with its 1st support chip opposite side The surface of (for example, thermoset resin layer) is fitted with the state keeping of stripping film.Therefore, by (being preferably it in the stripping film Lift-off processing face) on coating thermoset resin layer formation composition etc. be used to form the composition, simultaneously of the layer for forming most surface layer It is dried as needed, so as to form the layer for forming most surface layer on stripping film in advance, one is contacted with stripping film in this layer Remaining each layer is laminated using any means in above-mentioned in the exposed surface of the opposite side of side, is formed as not removing stripping film and protecting The state of fitting is held, thus also can obtain the 1st protective film formation piece.
Embodiment
Hereinafter, more specific detail is carried out to the present invention in conjunction with specific embodiments.It should be noted that the present invention is complete It is not limited entirely by embodiment described below.
Ingredient for the manufacture of thermoset resin layer formation composition is as follows.
Component of polymer
Component of polymer (A) -1：Make butyl acrylate (hereinafter referred to as " BA ") (55 mass parts), methyl acrylate (with Under be abbreviated as " MA ") (10 mass parts), glycidyl methacrylate (hereinafter referred to as " GMA ") (20 mass parts) and propylene Acrylic resin (the weight average molecular weight that sour 2- hydroxy methacrylates (hereinafter referred to as " HEA ") (15 mass parts) copolymerization forms 800000th, -28 DEG C of glass transition temperature).
Epoxy resin
Epoxy resin (B1) -1：Liquid bisphenol F types epoxy resin (Mitsubishi chemical Co., Ltd's system " YL983U ")
Epoxy resin (B1) -2：Multifunctional aromatic type epoxy resin (Nippon Kayaku K. K's system " EPPN-502H ")
Epoxy resin (B1) -3：Dicyclopentadiene type epoxy resin (DIC corporations " EPICLON HP-7200 ")
Thermal curing agents
Thermal curing agents (B2) -1：Novolak phenolics (Showa Denko K. K's system " BRG-556 ")
Curing accelerator
Curing accelerator (C) -1：2- phenyl -4,5- bishydroxymethyls imidazoles (Shikoku Chem's systems “Curezol 2PHZ-PW”)
Packing material
Packing material (D) -1：Through epoxy group modified spherical silicon dioxide (Admatechs Co. Ltd. systems " Adamano YA050C-MKK”)
[Production Example 1]
(manufacture of resin of binding property (I-2a))
Using 2-EHA (hereinafter referred to as " 2EHA ") (80 mass parts), HEA (20 mass parts) as copolymerization The raw material of object carries out polymerisation, results in acrylic polymer.
2- methacryloxyethyls isocyanates (hereinafter referred to as " MOI ") is added in into the acrylic polymer (22 mass parts are about 80 moles of % relative to HEA) carries out addition reaction in 48 hours in air draught in 50 DEG C, thus The resin of binding property (I-2a) of target is arrived.
[embodiment 1]
<The manufacture of 1st protective film formation piece>
(manufacture of thermoset resin layer formation composition)
By component of polymer (A) -1, epoxy resin (B1) -1, epoxy resin (B1) -2, epoxy resin (B1) -3, heat cure Agent (B2) -1, curing accelerator (C) -1 and packing material (D) -1 are so that the ratio of their content reaches the value shown in table 1 Mode be dissolved or dispersed in methyl ethyl ketone, be stirred in 23 DEG C, result in as thermoset resin layer formation combine The solid component concentration of object is the resin layer formation composition (III-1) of 55 mass %.It should be noted that containing in table 1 The record for having the "-" in one column of ingredient represents not contain the ingredient in thermoset resin layer formation composition.
(manufacture of the 1st adhesive composition)
It is added in relative to the resin of binding property (I-2a) (100 mass parts) obtained in Production Example 1 as isocyanates The toluene di-isocyanate(TDI) trimer addition product (TOSOH Co., Ltd's system " Coronate L ") of the trimethylolpropane of crosslinking agent (0.5 mass parts), are stirred in 23 DEG C, and it is 30 matter to result in as the solid component concentration of the 1st adhesive composition Measure the 1st adhesive composition (I-2) of %.It should be noted that it is somebody's turn to do the cooperation number in " manufacture of the 1st adhesive composition " It is solid constituent scaled value.
(manufacture of the 1st protective film formation piece)
Stripping to carry out lift-off processing is being handled the single side that polyethylene terephthalate is film-made by organosilicon Above-mentioned lift-off processing face coating obtained above the from film (38 μm of Lindeke Co., Ltd's system " SP-PET381031 ", thickness) 1 adhesive composition carries out 2 minutes heat dryings in 120 DEG C, thus forms the 1st adhesive phase of 60 μm of thickness.
Then, it is bonded in the exposed surface of the 1st adhesive phase as the 1st base material and stacks gradually polyolefin film (25 μ of thickness M), adhesive layer (2.5 μm of thickness), polyethylene terephthalate film (50 μm of thickness), adhesive layer (2.5 μm of thickness) and The stacked film of 105 μm of thickness that polyolefin film (25 μm of thickness) forms, results in the 1st support chip.
Stripping to carry out lift-off processing is being handled the single side that polyethylene terephthalate is film-made by organosilicon Above-mentioned lift-off processing face from film (38 μm of Lindeke Co., Ltd's system " SP-PET381031 ", thickness) applies heat obtained above Thermosetting resin layer formation composition carries out drying in 2 minutes in 100 DEG C, has thus made the thermosetting resin film of 40 μm of thickness (thermoset resin layer).
Then, stripping film is removed from the 1st adhesive phase of the 1st support chip obtained above, in the 1st adhesive phase Exposed surface is bonded the exposed surface of thermosetting resin film obtained above, has obtained the 1st base material, the 1st adhesive phase, thermosetting resin The 1st protective film formation piece that layer and stripping film stack gradually on their thickness direction.
<The evaluation of thermosetting resin film>
(shear viscosity (V1) of thermosetting resin film and the measure of Δ t1)
Other than having used thermoset resin layer formation composition obtained above and having made its coating amount difference, utilize Identical method has made the thermosetting resin film of 500 μm of thickness during with manufacturing above-mentioned 1st protective film formation piece.
Then, by thermosetting resin film production diameter 25mm, the evaluation sample of 500 μm of thickness, which is set In shear viscosity measurement device.At this point, in shear viscosity measurement device, the setting position of sample is protected prior to 70 DEG C in advance Said sample is placed in the setting position of the state, and is depressed from the upper surface of sample and measure fixture by temperature, thus consolidates sample Surely it is arranged on above-mentioned setting position.
Keeping the state, temperature in use control system adds sample in 130 DEG C of set temperature after 5 minutes Heat.It is made to be solidified to form solidfied material after uncured said sample softening is made as a result,.The heating speed of sample at this time Spend is 10 DEG C/minute.Then, measure the sample softened to as caused by heating it is cured during, in shear velocity 1s-1Under The viscosity of sample, and Δ t1 is obtained, result is 550 seconds.The results are shown in Table 3.In table 3, taken passages in combination from 130 DEG C Set temperature under start the temperature of the heating time heated to sample and the sample at the corresponding moment.It in addition, will at this time The relationship of above-mentioned heating time of sample, temperature and shear viscosity (V1) are shown in Fig. 6.In the heating process, with the time By having the outside that powder trickles down the setting position of sample, according to the phenomenon it has been confirmed that sample fully cures and most end form Into gel.
(bubble of the 1st protective film contains the confirmation of inhibition)
Using pressurized, heated solidification equipment (Lindeke Co., Ltd's system " RAD-9100 "), protected to the obtained above 1st Thermoset resin layer (thermosetting resin film) side of film formation piece apply the pressure side of 0.5MPa at 130 DEG C of set temperature plus Heat 2 hours after making thermoset resin layer (thermosetting resin film) softening, makes it be solidified to form the 1st protective film.
Then, the 1st protective film shape of the cured completion of thermoset resin layer is taken out from above-mentioned pressurized, heated solidification equipment Into with piece, and the 1st protective film is observed using light microscope.As a result, the 1st protective film does not contain bubble completely. The results are shown in Table 3.
<The manufacture of 1st protective film formation piece, the evaluation of thermosetting resin film>
[embodiment 2~7, comparative example 1~3]
In addition to make thermoset resin layer formation composition containing ingredient and content as shown in table 1 or 2 other than, with Embodiment 1 has similarly manufactured the 1st protective film formation piece, and thermosetting resin film is evaluated.
As a result, in embodiment 2~7, the Δ t1 of sample is 520~1780 seconds, and the 1st protective film does not contain gas completely Bubble, but in comparative example 1~3, the Δ t1 of sample is 0 or 320 second, and the 1st protective film contains bubble.These results are shown in table 3 Or 4, and the result of Examples 1 to 2 and comparative example 1 is additionally shown in Fig. 6.
[table 1]
[table 2]
[table 3]
[table 4]
From the above results, in the embodiment 1 that the Δ t1 of thermosetting resin film is 520 seconds or more (520~1780 seconds) In~7, the 1st protective film does not contain bubble completely.It is believed that in these embodiments, until the curing of thermosetting resin film Until end, it can be ensured that the low time-bands long enough of the shear viscosity (V1) of thermosetting resin film, therefore during this period, thermosetting property Bubble in resin film has all been discharged to external.
In contrast, in comparative example 1~3, contain bubble in the 1st protective film.It is believed that in these comparative examples, Until the curing of thermosetting resin film terminates, it is completely absent the shear viscosity (V1) of the thermosetting resin film low time The low time-bands of the shear viscosity (V1) of band or thermosetting resin film are short, thus during this period, the gas in thermosetting resin film Some is steeped directly to left behind.
Industrial applicibility
What the present invention can be applied to use in flip-chip installation method has partly leading for convex block in connection welding disk The manufacture of body chip etc..

Claims (3)

1. a kind of thermosetting resin film is used to be pasted onto the surface with convex block of semiconductor wafer and passes through carry out heat cure And the 1st protective film is formed on the surface, wherein,
When so that the thermosetting resin film before curing is heated up with 10 DEG C/minute of heating rate, in shear velocity 1s-1Under it is viscous The time that degree reaches below 100000Pas is 500 seconds or more.
2. a kind of 1st protective film formation piece, has thermosetting described in claim 1 on a side surface of the 1st support chip Property resin film.
3. a kind of forming method of 1st protective film, this method include：By to thermosetting resin film described in claim 1 Heat cure is brought it about while pressurization with the pressure of more than 0.1Pa and forms the 1st protective film.
CN201680061246.7A 2015-11-04 2016-11-02 The forming method of thermosetting resin film, the 1st protective film formation piece and the 1st protective film Pending CN108140586A (en)

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